CN113512033B

CN113512033B - Phenoxazine and phenothiazine covalent triazine framework material, and preparation method and application thereof

Info

Publication number: CN113512033B
Application number: CN202110550453.1A
Authority: CN
Inventors: 杜亚; 张悦; 张瑛頔; 刘玉婷
Original assignee: Nanjing Tech University
Current assignee: Nanjing Tech University
Priority date: 2021-05-19
Filing date: 2021-05-19
Publication date: 2023-06-16
Anticipated expiration: 2041-05-19
Also published as: CN113512033A

Abstract

The invention discloses a phenoxazine or phenothiazine covalent triazine frame material, a preparation method and application thereof. The phenoxazine or phenothiazine covalent triazine framework material is prepared by the following method: ion fusion reaction is carried out on phenoxazine or phenothiazine dicyano derivative and zinc chloride, water and acid are used for washing after the reaction is finished, and the obtained solid product is the phenoxazine or phenothiazine covalent triazine frame material. The structure of the phenoxazine or phenothiazine covalent triazine frame material is shown in the following formula (I):

the phenoxazine or phenothiazine covalent triazine frame material prepared by utilizing the ion melting method has high specific surface area. When used as the anode material of the lithium ion battery, the material has the advantages of high voltage, high capacity, good multiplying power performance and the like, and has good application prospect in novel high-performance organic electrode materials.

Description

Phenoxazine and phenothiazine covalent triazine framework material, and preparation method and application thereof

Technical Field

The invention belongs to the field of organic synthesis and organic functional materials, and particularly relates to a phenoxazine or phenothiazine dicyano derivative and a phenoxazine or phenothiazine covalent triazine frame material, and a preparation method and application thereof. The application is application of a phenoxazine or phenothiazine covalent triazine frame material in the related field of energy, and in particular relates to synthesis of a phenoxazine or phenothiazine dicyano derivative and a phenoxazine or phenothiazine covalent triazine frame material and application of the phenoxazine or phenothiazine covalent triazine frame material in a lithium ion battery anode material.

Background

The lithium ion battery is used as a chargeable and dischargeable secondary battery, and has the advantages of higher energy and power density, longer service life and the like, so that the lithium ion battery is successfully applied to various energy storage fields since development. The positive electrode material is an important factor restricting the increase in energy density of the battery. Compared with the traditional positive electrode material (transition metal oxide), the organic positive electrode material (comprising carbonyl compounds, conductive polymers, free radical compounds and the like) has been widely applied to the positive electrode material of the lithium ion battery due to the characteristics of available raw materials, various structures, environmental friendliness and the like. However, the existing organic materials have limited applications due to the disadvantages of poor conductivity, low redox potential, and dissolution in organic electrolytes.

The covalent triazine skeleton material is a porous material with good chemical stability and thermal stability, and the skeleton of the covalent triazine skeleton material contains rich nitrogen elements, so that the surface of the material has polarity, and the covalent triazine skeleton material has great practical application prospect in the fields of gas adsorption separation, heterogeneous catalysis, photoelectric technology and the like. The diheteroanthracene derivatives are aromatic heterocyclic structures containing electron-rich nitrogen atoms and oxygen (or sulfur) atoms, and easily lose one electron to form free radical positive ions. The N-type covalent triazine framework material is used as a positive electrode material of a lithium ion battery, has higher theoretical specific capacity, but limits the actual utilization of active sites due to large inter-particle interface steric hindrance and low intrinsic conductivity, and has lower actual capacity; when the polymer or the small molecule based on the diheteroanthracene is used as a battery positive electrode material, typical P-type materials are expressed, and the polymer or the small molecule based on the diheteroanthracene has the advantages of high voltage, high cycle stability and the like when being used as the battery positive electrode material, but the theoretical specific capacity is lower. Therefore, the design of a novel P-N composite dithionthracene (also called phenoxazine or phenothiazine) covalent triazine skeleton material for a battery positive electrode material has important significance and is very challenging.

Disclosure of Invention

Aiming at the defects in the prior art, the main purpose of the invention is to provide a phenoxazine or phenothiazine dicyano derivative and a preparation method thereof, and a phenoxazine or phenothiazine covalent triazine frame material and a preparation method and application thereof.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides a phenoxazine or phenothiazine dicyano derivative, which has a structure shown as a formula (II):

wherein X is selected from O or S, and R is selected from any one of straight-chain alkyl, branched-chain alkyl and aromatic ring radical. The embodiment of the invention also provides a preparation method of the phenoxazine dicyano derivative, which comprises the following steps:

(1) Reacting a first uniformly mixed reaction system containing 4-hydroxy-3-nitrobenzonitrile, a palladium catalyst, a reducing agent and a first solvent for 12-16 hours at 78 ℃ in a protective atmosphere to prepare 4-hydroxy-3-aminobenzonitrile;

(2) Reacting a second uniformly mixed reaction system containing the 4-hydroxy-3-aminobenzonitrile, 3, 4-difluorobenzonitrile, a first alkaline substance and a second solvent for 8-12 hours at 100 ℃ in a protective atmosphere to prepare 2, 7-dicyano-10H-phenoxazine;

(3) And (3) reacting a third mixed reaction system containing the 2, 7-dicyano-10H-phenoxazine, a second alkaline substance, halogenated hydrocarbon and a third solvent at 25-35 ℃ for 5-10 hours to prepare the phenoxazine dinitrile monomer derivative.

The embodiment of the invention also provides a preparation method of the phenothiazine dicyano derivative, which comprises the following steps:

(1) Reacting a uniformly mixed reaction system containing 2-chlorophenothiazine, liquid bromine and acetic acid for 24 hours at room temperature in a protective atmosphere to prepare 2-chloro-7-bromo-10H-phenothiazine;

(2) And reacting a first mixed reaction system comprising the 2-chloro-7-bromo-10H-phenothiazine, a first alkaline substance, halogenated hydrocarbon and a first solvent for 1 hour at room temperature in a protective atmosphere to obtain the 2-chloro-7-bromo-10-R-phenothiazine.

(3) And (3) reacting a second mixed reaction system containing the 2-chloro-7-bromo-10-R-phenothiazine, cuprous cyanide and a second solvent for 12-24 hours at 140-150 ℃ to prepare the 2, 7-dicyano-10-R-phenothiazine.

The embodiment of the invention also provides a phenoxazine or phenothiazine covalent triazine frame material, which has a structure shown in a formula (I):

the embodiment of the invention also provides a preparation method of the phenoxazine or phenothiazine covalent triazine frame-based material, which comprises the following steps:

The ratio of the phenoxazine or phenothiazine dicyano derivative to the zinc chloride is 1:1-20, and the reaction conditions of the ion melting reaction are as follows: in a vacuum closed environment, the temperature is programmed to 350-600 ℃ and the reaction is carried out for 24-72 hours.

The embodiment of the invention also provides the application of the phenoxazine or phenothiazine covalent triazine frame material in the anode material of the lithium ion battery.

The embodiment of the invention also provides a lithium ion battery anode which at least comprises the phenoxazine or phenothiazine covalent triazine frame material.

The embodiment of the invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode comprises the positive electrode of the lithium ion battery.

The embodiment of the invention also provides a preparation method of the lithium ion battery, which comprises the following steps:

and uniformly mixing the phenoxazine or phenothiazine covalent triazine frame material, a conductive agent and a binder, then applying the obtained mixture to a conductive current collector to form a battery anode, and then assembling the battery anode, a negative electrode and an electrolyte into a lithium ion battery.

Compared with the prior art, the invention has the beneficial effects that: the preparation method provided by the invention takes commercial 4-hydroxy-3-nitrobenzonitrile as a raw material, firstly reduces intramolecular nitro, then reacts with 3, 4-difluorobenzonitrile under alkaline conditions to generate intermolecular aryl nucleophilic substitution reaction, and then generates intramolecular nucleophilic substitution reaction ring closure to obtain 2, 7-dicyano-10-R-phenoxazine. Commercial 2-chlorophenothiazine is taken as raw material, brominated and then methyl are carried out, and finally cyanide is adopted to replace halogen The element is 2, 7-dicyano-10-R-phenothiazine. The obtained 2, 7-dicyano-10-R-phenoxazine and/or 2, 7-dicyano-10-R-phenothiazine undergo cyano trimerization under the condition of molten zinc chloride to obtain the phenoxazine or phenothiazine covalent triazine frame material. The 2, 7-dicyano-10-R-phenoxazine/phenothiazine prepared by the method has the advantages of simple operation of the reaction process, simple synthetic route and high reaction yield, and the compounds provide important synthesis precursors for covalent triazine frame materials; the covalent triazine frame material based on phenoxazine or phenothiazine has high specific surface area, good thermal stability and high oxidation-reduction potential (-3.5V vs Li/Li) ⁺ ) And a plurality of pairs of redox peaks, so that the phenoxazine or phenothiazine covalent triazine framework material prepared by the method can be applied to a lithium ion battery anode material, and has good application prospect in the field of functional organic materials.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a nuclear magnetic resonance spectrum of 3-amino-4-hydroxybenzonitrile prepared in step (1) in example 1 of the present invention;

FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of 2, 7-dicyano-10H-phenoxazine prepared in step (2) of example 1 of the present invention;

FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of 2, 7-dicyano-10-methylphenoxazine prepared in step (3) of example 1 of the present invention;

FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of 2-chloro-7-bromo-10H-phenothiazine prepared in step (1) of example 2 of the present invention;

FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of 2-chloro-7-bromo-10-methyl-phenothiazine prepared in step (2) of example 2 of the present invention;

FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of 2, 7-dicyano-10-methylphenothiazine prepared in step (3) of example 2 of the present invention;

FIG. 7 is an infrared spectrum of a phenoxazine or phenothiazine covalent triazine framework material obtained in examples 11-12 of the present invention;

FIG. 8 is a powder X-ray diffraction pattern of the phenoxazine or phenothiazine covalent triazine framework material obtained in example 3 of the present invention;

FIG. 9 is a nitrogen adsorption desorption isotherm plot of the phenoxazine or phenothiazine covalent triazine framework material obtained in example 3 of the present invention.

Fig. 10 is a graph of the cycling stability test of a phenoxazine and/or phenothiazine covalent organic framework material cell in example 8 of the present invention. After the phenoxazine and/or phenothiazine covalent organic framework material is circulated for 100 circles, the specific discharge capacities can still be respectively kept at 159mAh/g and 126mAh/g, the capacity retention rates are respectively 82% and 92% (after the phenoxazine and/or phenothiazine covalent organic framework material is circulated for 10 circles and is stabilized, the initial specific discharge capacities are respectively 192mAh/g and 136 mAh/g).

FIG. 11 is a cyclic voltammogram of a cell of a phenoxazine or phenothiazine covalent triazine framework material in example 8 of the present invention. The phenoxazine covalent triazine frame material shows a certain pseudocapacitance lithium storage mechanism, while the phenothiazine covalent triazine frame material shows three pairs of redox peaks, namely E of triazine ring _O1/R1 E at about 2.3/2.5V, phenothiazine first potential _O2/R2 E at about 3.6/3.5V and phenothiazine second potential _O3/R3 ～4.2/4.3V。

FIG. 12 is an electrochemical impedance spectrum of a cell of the phenoxazine and/or phenothiazine covalent organic framework material of example 8 of the present invention. The charge transfer resistances of the phenoxazine and/or phenothiazine covalent organic framework materials are 210 Ω and 310 Ω, respectively.

Detailed Description

In view of the shortcomings of the prior art, the inventor of the present application has long studied and put forward a great deal of practice, and the technical solution of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

An aspect of an embodiment of the present invention provides a phenoxazine or phenothiazine dicyano derivative having a structure as shown in formula (II):

wherein X is selected from O or S, and R is selected from any one of straight-chain alkyl, branched-chain alkyl and aromatic ring radical.

In the invention, the phenoxazine dicyano derivative is 2, 7-dicyano-10-R-phenoxazine, and the phenothiazine dicyano derivative is 2, 7-dicyano-10-R-phenothiazine.

In some more specific embodiments, the phenoxazine dicyano derivative has a structure as shown in formula (III):

wherein R is selected from any one of straight-chain alkyl, branched-chain alkyl and aromatic ring, preferably any one of methyl, ethyl, isopropyl, phenyl and naphthyl.

In some more specific embodiments, the phenothiazine dicyano derivative has a structure as shown in formula (IV):

An aspect of embodiments of the present invention also provides a phenoxazine or phenothiazine covalent triazine framework material having a structure as shown in formula (I):

In some more specific embodiments, the specific surface area of the phenoxazine covalent triazine framework material is 1131m ² /g, pore size of 1.29nm; the specific surface area of the phenothiazine covalent triazine frame material is 14m ² And/g, pore size of 4.22nm.

In the invention, the phenoxazine covalent triazine frame material with the structure shown in the formula (I) is named as DCPO-CTF (X=O, R= -CH) ₃ A.); phenothiazine covalent triazine framework material is named DCPT-CTF (x=s, r= -CH) ₃ )。

In another aspect of the embodiment of the present invention, there is provided a method for preparing a phenoxazine dicyano derivative, including:

(3) Reacting a third mixed reaction system comprising the 2, 7-dicyano-10H-phenoxazine, a second alkaline substance, halogenated hydrocarbon and a third solvent at 25-35 ℃ for 5-10 hours to prepare the phenoxazine dinitrile derivative.

In some more specific embodiments, the molar ratio of the 4-hydroxy-3-nitrobenzonitrile, palladium catalyst to reducing agent in step (1) is from 1:0.1:20 to 1:0.1:40;

further, the reducing agent is hydrazine hydrate.

Further, the mass concentration of the hydrazine hydrate is 80wt%.

Further, the first solvent includes an alcohol solvent or a mixed solution of an alcohol solvent and a high-solubility solvent, and is not limited thereto.

Further, the alcohol solvent includes any one or a combination of two of methanol and ethanol, and is not limited thereto.

Still further, the high-solubility solvent includes any one or a combination of two of ethyl acetate and chloroform, and is not limited thereto.

Further, the palladium catalyst includes a palladium carbon catalyst, and is not limited thereto.

Still further, the palladium on carbon catalyst includes: palladium 5wt%, the remainder comprising activated carbon.

In some more specific embodiments, the method of making further comprises: and after the reaction of the first mixed reaction system is finished, filtering and purifying the obtained mixture.

Further, the purification treatment comprises extraction and column chromatography separation and purification treatment.

In some more specific embodiments, the molar ratio of 4-hydroxy-3-aminobenzonitrile, 3, 4-difluorobenzonitrile, first basic material in step (2) is from 1:1:1.5 to 1:1:2.5.

Further, the first alkaline substance includes potassium hydroxide or potassium carbonate, and is not limited thereto.

Further, the second solvent includes dimethyl sulfoxide or N, N-dimethylformamide, and is not limited thereto.

In some more specific embodiments, the method of making further comprises: and after the reaction of the first uniform mixed reaction system is finished, washing, drying and purifying the obtained mixture.

Further, the purification treatment includes: the dried product was stirred in ethyl acetate for about 5min and the resulting solid product was filtered.

In some more specific embodiments, the molar ratio of 2, 7-dicyano-10H-phenoxazine, second basic material, halogenated hydrocarbon in step (3) is 1:1.5:2.

Further, the halogenated hydrocarbon includes r—x, wherein X is selected from any one of F, cl, br, I, R is selected from any one of straight-chain alkyl, branched-chain alkyl, aromatic ring group, preferably, the R is selected from any one of methyl, ethyl, isopropyl, phenyl, naphthyl, and is not limited thereto.

Further, the second alkaline substance includes sodium hydride or potassium carbonate, and is not limited thereto.

Further, the third solvent includes N, N-dimethylformamide or dimethylsulfoxide, and is not limited thereto.

Further, the protective atmosphere includes a nitrogen atmosphere or an argon atmosphere, and is not limited thereto.

In some more specific embodiments, the method of preparing a phenoxazine dicyano derivative comprises:

(1) Dissolving 4-hydroxy-3-nitrobenzonitrile in an alcohol solvent, adding a solid palladium catalyst, taking hydrazine hydrate as a reducing agent, and refluxing for 12 hours at 78 ℃. After the reaction is finished, the diatomite filter system is adopted, the filtrate is dried in a spinning way, water is added, then ethyl acetate is used for extraction and collection of an organic phase, and finally, column chromatography purification is carried out, so that the 4-hydroxy-3-aminobenzonitrile is obtained.

(2) Dissolving 4-hydroxy-3-aminobenzonitrile, 3, 4-difluorobenzonitrile and potassium hydroxide in dimethyl sulfoxide, heating to 100 ℃, adding water into the system for treatment after the reaction is completed, filtering to obtain a solid, drying, stirring in ethyl acetate, and filtering to obtain the solid which is an intermediate product 2, 7-dicyano-10H-phenoxazine.

(3) 2, 7-dicyano-10H-phenoxazine, sodium hydride, halohydrocarbon (R-X) and N, N-dimethylformamide react under the protection of nitrogen, water is added into a system for treatment after the reaction is finished, and the 2, 7-dicyano-10-R-phenoxazine is obtained by filtering.

Preferably, in the step (1), the alcohol solvent is methanol or ethanol or a mixed solution of alcohol and a high-solubility solvent.

Further, in the step (1), the solid palladium catalyst adopts palladium carbon, wherein the solid palladium catalyst comprises 5wt% of palladium, and the rest part comprises active carbon.

Further, in the step (1), the reducing agent is 80% hydrazine hydrate.

Further, in the step (2), the molar ratio of the 4-hydroxy-3-aminobenzonitrile to the 3, 4-difluorobenzonitrile to the first alkaline substance is 1:1:1.5 to 1:1:2.5.

Further, in the step (3), the molar ratio of the 2, 7-dicyano-10H-phenoxazine to the second basic material and the halogenated hydrocarbon is 1:1.5:2.

In another aspect of the embodiment of the present invention, there is provided a method for preparing a phenothiazine dicyano derivative, including:

In some more specific embodiments, the molar ratio of 2-chloro-7-bromo-10H-phenothiazine, first basic substance, and halogenated hydrocarbon in step (2) is 1:1.5:2.

Further, the first alkaline substance includes sodium hydride or potassium carbonate, and is not limited thereto.

Further, the first solvent includes N, N-dimethylformamide or dimethylsulfoxide, and is not limited thereto.

In some more specific embodiments, the molar ratio of 2-chloro-7-bromo-10-R-phenothiazine to cuprous cyanide in step (3) is 1:2.4.

The second solvent comprises N, N-dimethylformamide and/or N-methylpyrrolidone.

The protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.

The preparation method further comprises the following steps: after the reaction of the second uniform mixed reaction system is completed, washing, drying and purifying the obtained mixture; preferably, the purification treatment comprises: and separating the product after the drying treatment by using column chromatography.

In another aspect of the embodiments of the present invention, there is provided a method for preparing a phenoxazine or phenothiazine covalent triazine framework material, comprising:

the ratio of the amount of the substances of the phenoxazine or phenothiazine dicyano derivative to the zinc chloride is 1:1-20, and the reaction conditions of the ion melting reaction are as follows: in a vacuum closed environment, the temperature is raised to 350-600 ℃ and the reaction is carried out for 24-72 hours.

In some more specific embodiments, the phenoxazine dicyano derivative is selected from 2, 7-dicyano-10-methylphenoxazine and the phenothiazine dicyano derivative is selected from 2, 7-dicyano-10-methylphenothiazine.

Further, the ratio of the amount of 2, 7-dicyano-10-methylphenoxazine and/or 2, 7-dicyano-10-methylphenothiazine to the amount of zinc chloride is 1:1-20.

In some more specific embodiments, the method of making further comprises: after the reaction is completed, the obtained mixture is subjected to filtration, washing and drying.

Further, the washing liquid used in the washing treatment comprises acid, distilled water and an organic solvent.

Further, the acid solution is hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 1-5 mol/L.

Further, the organic solvent is tetrahydrofuran or dichloromethane. And is not limited thereto.

Further, the drying process includes: vacuum drying at 50-100 deg.c for 12-24 hr.

In some more specific embodiments, the method of making a phenoxazine or phenothiazine covalent triazine framework material comprises:

(1) Sealing 2, 7-dicyano-10-methylphenoxazine and/or 2, 7-dicyano-10-methylphenothiazine with zinc chloride under vacuum;

(2) And (3) placing the mixed system prepared in the step (1) in a high-temperature program oven, raising the temperature from room temperature to 450 ℃ at 3 ℃/min, preserving the temperature for 48 hours, and naturally cooling to the room temperature.

(3) And after the heating reaction is finished, cooling the reaction vessel to room temperature, collecting black solid products, filtering and washing with hydrochloric acid, tetrahydrofuran and dichloromethane respectively, and then drying in vacuum to obtain the covalent triazine frame material.

Further, the mass ratio of the 2, 7-dicyano-10-methylphenoxazine and/or the 2, 7-dicyano-10-methylphenothiazine to the zinc chloride in the step (1) is 1:1-20.

Further, the temperature of step (2) is 450 ℃, but is not limited thereto.

Further, the concentration of the hydrochloric acid solution in the step (3) is 1mol/L, but is not limited thereto.

Further, the temperature of the vacuum drying in the step (3) is 120 ℃, and the drying time is 12 hours.

In some embodiments, the preparation method may comprise: under the ion heating condition, placing the 2, 7-dicyano-10-methyl phenoxazine and/or the mixed system of 2, 7-dicyano-10-methyl phenothiazine and zinc chloride in a 10mL ampoule bottle, sealing in a vacuum state, placing in a high-temperature programming oven, heating to 450 ℃, maintaining the temperature for 48 hours, naturally cooling, collecting black solid, filtering and washing with hydrochloric acid and tetrahydrofuran, and vacuum drying at 120 ℃ for 12 hours to obtain the black solid, namely the phenoxazine or phenothiazine covalent triazine frame material.

In another aspect of embodiments of the present invention, there is also provided a phenoxazine or phenothiazine covalent triazine framework material prepared by the foregoing method.

In another aspect, the embodiment of the invention also provides the application of the phenoxazine or phenothiazine covalent triazine frame material in the anode of a lithium ion battery.

In the invention, the phenoxazine or phenothiazine covalent triazine framework material has redox activity when used for the anode research of lithium ion batteries.

In another aspect, the present invention provides a positive electrode of a lithium ion battery, which at least comprises the phenoxazine or phenothiazine covalent triazine frame material.

In another aspect, the embodiment of the invention further provides a lithium ion battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode comprises the positive electrode of the lithium ion battery.

Another aspect of the embodiment of the present invention also provides a method for preparing a lithium ion battery, including: and uniformly mixing the phenoxazine or phenothiazine covalent triazine frame material, a conductive agent and a binder, then applying the obtained mixture to a conductive current collector to form a battery anode, and then assembling the battery anode, a negative electrode and an electrolyte into the lithium ion battery.

Further, the conductive current collector includes an aluminum foil and/or a carbon-coated aluminum foil, and is not limited thereto.

Further, the lithium ion battery includes a button battery, and is not limited thereto.

In the invention, 4-hydroxy-3-nitrobenzonitrile, 3, 4-difluorobenzonitrile and 2-chlorophenothiazine are taken as raw materials, and the reaction route for synthesizing phenoxazine or phenothiazine dicyano derivatives is shown as follows:

The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.

The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.

Example 1

(1) Synthesis of 3-amino-4-hydroxybenzonitrile:

4-hydroxy-3-nitrobenzonitrile (20 mmol,3.28 g) and palladium on carbon (55% water) (2 mmol, 470 mg) were accurately weighed into a 250mL pre-dried three neck round bottom flask. Under nitrogen atmosphere, 100mL of anaerobic ethanol was added while stirring. After the system was dissolved, hydrazine hydrate (85 wt%) (200 mmol,11.12 mL) was added dropwise to the system and refluxed at 78℃for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the reaction mixture was filtered through celite to give a filtrate, which was dried by spinning, 20mL of water was added, and the organic phase was collected by extraction with ethyl acetate (3×20 mL). The mixture was separated and purified by column chromatography to give 2.15g of 3-amino-4-hydroxybenzonitrile in 80% yield. The nuclear magnetic resonance hydrogen spectrum is shown in figure 1, ¹ H NMR(400MHz，DMSO-d ₆ )δppm 10.23(s，1H)，6.86，6.83(d，2H)，6.75，6.73(s，1H)，4.99(s，2H).

(2) Synthesis of 2, 7-dicyano-10H-phenoxazine

3-amino-4-hydroxybenzonitrile (20 mmol,2.68 g), 3, 4-difluorobenzonitrile (20 mmol, 2.78 g), potassium hydroxide (40 mmol,2.24 g) were accurately weighed into a 250mL three-necked flask, 100mL of dimethyl sulfoxide was added to the system under stirring in a nitrogen atmosphere, and the temperature was raised to 100℃for reaction overnight. After the reaction is finished, cooling to room temperature, adding 50mL of water into the system, gradually precipitating dark green solid from the system, filtering, collecting a filter cake, and vacuumizing and drying. The dried product was further washed with ethyl acetate and filtered to give 3.5g of 2, 7-dicyano-10H-phenoxazine as a product in 75% yield. The melting point is 300.2-300.4 ℃. The nuclear magnetic resonance hydrogen spectrum is shown in figure 2As shown in the drawing, ¹ H NMR(400MHz，DMSO-d ₆ )δppm 9.22(s，1H)，7.21(dd，J＝8.0，1.6Hz， 1H)，7.10(dd，J＝8.4，1.6Hz，1H)，7.04(d，J＝1.2Hz，1H)，6.75(d，J＝8.0Hz，1H)， 6.35(d，J＝1.6Hz，1H)6.52(d，J＝8.4Hz，1H). ¹³ C NMR(100MHz，DMSO-d ₆ )δ ppm 146.41，142.05，136.11，131.75，130.31，126.91，118.81，118.43，118.06，116.14， 116.06，113.76，106.71，101.94.HRMS(ESI)m/z：[M+H] ⁺ calcd for C ₁₄ H ₇ N ₃ O 234.0667；found 234.0659.

(3) Synthesis of 2, 7-dicyano-10-methylphenoxazine

2, 7-dicyano-10H-phenoxazine (10 mmol,2.33 g), sodium hydride (15 mmol,300 mg) was taken in a 250mL three-necked round bottom flask, 100mL of super-dry solvent N, N-dimethylformamide was added under stirring under nitrogen atmosphere, methyl iodide (20 mmol,1.24 mL) was slowly added dropwise after the system was dissolved, and the reaction was carried out at room temperature overnight. After the reaction, 50mL of water is added for stirring, a large amount of brown solid is precipitated in the system, the mixture is filtered, a filter cake is collected, and the mixture is vacuumized and dried. The drained product was then dissolved in ethyl acetate, filtered, and rinsed with ethyl acetate multiple times to give 1.73g of the dark gray product in 70% yield. Melting point 278-279 ℃. The nuclear magnetic resonance hydrogen spectrum is shown in figure 3, ¹ H NMR(400MHz，DMSO-d ₆ )δppm 7.38(dd，J＝8.4，1.6Hz，1H)，7.25(dd， J＝8.0，1.6Hz，1H)，7.21(d，J＝1.6Hz，1H)，7.15(d，J＝1.6Hz，1H)，6.85(d，J＝ 8.4Hz，1H)，6.84(d，J＝8.0Hz，1H)，3.08(s，3H). ¹³ C NMR(100MHz，DMSO-d ₆ )δ ppm 147.86，143.56，137.93，133.911，130.46，127.58，118.63，118.62，117.67， 115.92(d，2C)，113.08，107.10，102.66，31.30.HRMS(ESI)m/z：[M+H] ⁺ calcd for C ₁₅ H ₉ N ₃ O 248.0824，found 248.0819.

Example 2

(1) Synthesis of 2-chloro-7-bromo-10H-phenothiazine

Accurately weigh 2-chlorophenothiazine (5 mmol,1.18 g) in a 100mL two-necked round bottom flask, under nitrogen, add 25mL of oxygen-free CH ₃ COOH, stirring and constant pressure drop Br ₂ (0.24 mL dissolved in 25mL CH) ₃ COOH), for 24 hours. After the reaction of the system is finished, adding Na into the system ₂ S ₂ SO ₃ Stirring the solution, adding NaOH solution, stirring, filtering, washing the filter cake with water, washing with cold isopropanol, and collecting the filter cake and drying. Repeated recrystallization with toluene gave a silvery white solid (1 g, 64%). The nuclear magnetic resonance hydrogen spectrum is shown in figure 4 ¹ H NMR(400MHz，DMSO-d ₆ )δppm 8.89(s，1H)，7.17(dd，J＝8.0，2.4 Hz，1H)，7.14(d，J＝2.0Hz，1H)6.94(d，J＝8.0Hz，1H)，6.80(dd，J＝8.0，2.0Hz， 1H)，6.67(d，J＝2.4Hz，1H)，6.58(d，J＝8.0Hz，1H).

(2) Synthesis of 2-chloro-7-bromo-10-methylphenothiazine

2-chloro-7-bromo-10H-phenothiazine (155.46 mg,0.5 mmol) was weighed accurately into a 10mL two-necked flask, 5mL of ultra-dry N, N-dimethylformamide was added under nitrogen, sodium hydride (30 mg, 0.75 mmol) was added after the raw materials were dissolved, stirred for half an hour, methyl iodide (1 mmol,0.062 mL) was added, and stirred at room temperature for 1 hour. After the reaction is finished, adding water, stirring, filtering, washing a filter cake with water, and collecting the filter cake for drying. A pale pink solid (130 mg, 80%) was obtained. The nuclear magnetic resonance hydrogen spectrum is shown in figure 5, ¹ H NMR(400MHz，DMSO-d ₆ )δppm 7.40 (m，2H)，7.17(d，J＝8.4Hz 1H)，7.02(dd，J＝8.0，2.0Hz 1H)，6.99(d，J＝2.0Hz 1H)，6.90(dd，J＝8.0，2.0Hz 1H)，3.29(s，3H).

(3) Synthesis of 2, 7-dicyano-10-methylphenothiazine

2-chloro-7-bromo-10-methylphenothiazine (1.5 mmol,487.4 mg) and cuprous cyanide (2.4 mmol, 322.4 mg) were accurately weighed into a pre-dried three-neck flask, 5mL of ultra-dry N, N-dimethylformamide was added under nitrogen, stirred, and the temperature was raised to 150℃for reaction for 24 hours. After the reaction is finished, cooling to room temperature, adding 30mL of 15% NaOH solution into the system, adding 50mL of 15% ammonia water, stirring, filtering, washing the filter cake with water, and drying. And finally purifying by column chromatography. Cyan powder (250 mg, 63%) was obtained. Melting point 204-206 deg.c. The nuclear magnetic resonance hydrogen spectrum is shown in figure 6, ¹ H NMR(400MHz，DMSO-d ₆ )δppm 7.67(dd，J＝ 8.5，2.0Hz，1H)，7.64(d，J＝1.9Hz，1H)，7.18(d，J＝8.1Hz，1H)，7.11-7.07(m，1H)， 7.06(m，2H)，3.36(s，3H). ¹³ C NMR(100MHz，Chloroform-d)δppm 149.39，145.78， 134.42，132.53，130.51，128.26，124.80，123.93，120.97，119.02，115.70(d，2C)， 114.72，106.35，36.14.HRMS(ESI)m/z：[M+H] ⁺ calcd for C ₁₅ H ₉ N ₃ S 264.0595，found 264.0578.

Example 3

(1) Synthesis of 3-amino-4-hydroxybenzonitrile:

4-hydroxy-3-nitrobenzonitrile (20 mmol,3.28 g), palladium on carbon (55% water) (2 mmol, 472 mg) was accurately weighed into a 250mL pre-dried three neck round bottom flask. Under nitrogen atmosphere, 100mL of anaerobic ethanol was added while stirring. After the system was dissolved, hydrazine hydrate (85 wt%) (200 mmol,11.12 mL) was added dropwise to the system and refluxed at 78℃for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the reaction mixture was filtered through celite to give a filtrate, which was dried by spinning, 20mL of water was added, and the organic phase was collected by extraction with ethyl acetate (3×20 mL). Separating and purifying by column chromatography to obtain 3-amino-4-hydroxy benzene2.15g of formonitrile with 80 percent yield. The nuclear magnetic resonance hydrogen spectrum is shown in figure 1, ¹ H NMR(400MHz，DMSO-d ₆ )δppm 10.23(s，1H)， 6.86，6.83(d，2H)，6.75，6.73(s，1H)，4.99(s，2H)

(2) Synthesis of 2, 7-dicyano-10H-phenoxazine

3-amino-4-hydroxybenzonitrile (20 mmol,2.68 g), 3, 4-difluorobenzonitrile (20 mmol, 2.78 g), potassium hydroxide (40 mmol,2.24 g) were accurately weighed into a 250mL three-necked flask, 100mL of dimethyl sulfoxide was added to the system under stirring in a nitrogen atmosphere, and the temperature was raised to 100℃for reaction overnight. After the reaction is finished, cooling to room temperature, adding 50mL of water into the system, gradually precipitating dark green solid from the system, filtering, collecting a filter cake, and vacuumizing and drying. The dried product was further washed with ethyl acetate and filtered to give 3.5g of 2, 7-dicyano-10H-phenoxazine as a product in 75% yield. The melting point is 300.2-300.4 ℃. The nuclear magnetic resonance hydrogen spectrum is shown in figure 2, ¹ H NMR(400MHz，DMSO-d ₆ )δppm 9.22(s，1H)，7.21(dd，J＝8.0，1.6Hz，1H)，7.10(dd，J＝8.4，1.6Hz，1H)，7.04(d，J＝1.2Hz，1H)，6.75(d，J＝8.0Hz，1H)， 6.35(d，J＝1.6Hz，1H)6.52(d，J＝8.4Hz，1H). ¹³ C NMR(100MHz，DMSO-d ₆ )δ ppm 146.41，142.05，136.11，131.75，130.31，126.91，118.81，118.43，118.06，116.14， 116.06，113.76，106.71，101.94.HRMS(ESI)m/z：[M+H] ⁺ calcd for C ₁₄ H7N ₃ O 234.0667；found 234.0659.

(3) Synthesis of 2, 7-dicyano-10-butylphenoxazine

2, 7-dicyano-10H-phenoxazine (116.5 mg,0.5 mmol), sodium hydroxide (168 mg,4.2 mmol) were taken in a 10mL round bottom flask and the solvent dimethylsulfoxide (5 mL) was added under nitrogen) 1-bromobutane (0.1 mL,0.85 mmol) was added slowly and stirred slowly at room temperature for 24 hours. After the reaction was complete, the reaction mixture was poured into water and stirred, filtered and the filter cake was collected and dried under vacuum. Further purification by column chromatography gave the product as a grey solid (100 mg, 69%). The melting point is 220.3-222.3 ℃. ¹ H NMR(400 MHz，Chloroform-d)δppm 7.33(dd，J＝8.4，2.0Hz，1H)，7.21(m，2H)，7.09(d，J＝ 2.0Hz，1H)，6.81(d，J＝8.4Hz，1H)，6.78(d，J＝8.4，1H)，3.45(t，2H)，1.61(m，2H)， 1.46(m，2H)，1.04(t，3H). ¹³ C NMR(100MHz，Chloroform-d)δppm 148.61，144.37， 137.04，133.22，130.38，127.85，119.10，118.93，118.73，116.74，115.07，112.15， 108.25，104.42，44.63，27.09，20.46，14.25.HRMS(ESI)m/z：[M+H] ⁺ calcd for C ₁₈ H ₁₅ N ₃ O 290.1293，found 290.1292.

Example 4

(1) Synthesis of 3-amino-4-hydroxybenzonitrile:

4-hydroxy-3-nitrobenzonitrile (20 mmol,3.28 g), palladium on carbon (55% water) (2 mmol, 472 mg) was accurately weighed into a 250mL pre-dried three neck round bottom flask. Under nitrogen atmosphere, 100mL of anaerobic ethanol was added while stirring. After the system was dissolved, hydrazine hydrate (85 wt%) (200 mmol,11.12 mL) was added dropwise to the system and refluxed at 78℃for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the reaction mixture was filtered through celite to give a filtrate, which was dried by spinning, 20mL of water was added, and the organic phase was collected by extraction with ethyl acetate (3×20 mL). The mixture was separated and purified by column chromatography to give 2.15g of 3-amino-4-hydroxybenzonitrile in 80% yield. The nuclear magnetic resonance hydrogen spectrum is shown in figure 1, ¹ H NMR(400MHz，DMSO-d ₆ )δppm 10.23(s，1H)， 6.86，6.83(d，2H)，6.75，6.73(s，1H)，4.99(s，2H)

(2) Synthesis of 2, 7-dicyano-10H-phenoxazine

3-amino-4-hydroxybenzonitrile (20 mmol,2.68 g), 3, 4-difluorobenzonitrile (20 mmol, 2.78 g), potassium hydroxide (40 mmol,2.24 g) were accurately weighed into a 250mL three-necked flask, 100mL of dimethyl sulfoxide was added to the system under stirring in a nitrogen atmosphere, and the temperature was raised to 100℃for reaction overnight. After the reaction is finished, cooling to room temperature, adding 50mL of water into the system, gradually precipitating dark green solid from the system, filtering, collecting a filter cake, and vacuumizing and drying. The dried product was further washed with ethyl acetate and filtered to give 3.5g of 2, 7-dicyano-10H-phenoxazine as a product in 75% yield. The melting point is 300.2-300.4 ℃. The nuclear magnetic resonance hydrogen spectrum is shown in figure 2, ¹ H NMR(400MHz，DMSO-d ₆ )δppm 9.22(s，1H)，7.21(dd，J＝8.0，1.6Hz， 1H)，7.10(dd，J＝8.4，1.6Hz，1H)，7.04(d，J＝1.2Hz，1H)，6.75(d，J＝8.0Hz，1H)， 6.35(d，J＝1.6Hz，1H)6.52(d，J＝8.4Hz，1H). ¹³ C NMR(100MHz，DMSO-d ₆ )δ ppm 146.41，142.05，136.11，131.75，130.31，126.91，118.81，118.43，118.06，116.14， 116.06，113.76，106.71，101.94.HRMS(ESI)m/z：[M+H] ⁺ calcd for C ₁₄ H ₇ N ₃ O 234.0667；found 234.0659.

(3) Synthesis of 2, 7-dicyano-10-butylphenoxazine

2, 7-dicyano-10H-phenoxazine (256.3 mg,1.10 mmol), bromobenzene (0.11 mL,1.00 mmol), pd (dba) was taken ₂ (35 mg,6 mol%), tri-tert-butylphosphine tetrafluoroborate (17 mg,6 mol%) and sodium tert-butoxide (111 mg,1.15 mmol) were dissolved in dry 1, 4-dioxane (3 mL). The system was degassed under nitrogen for 5 minutes. The reaction mixture was then stirred at 100 ℃ for 14 hours. After cooling to room temperature, deionized water (50 mL) was added sequentially, saturated Na ₂ SO ₃ Solution (15 mL) and dichloromethane (50 mL). Using dichloromethane3 x 10 ml) of the aqueous phase. The combined organic phases were dried over anhydrous magnesium sulfate and the solvent was removed in vacuo. The crude product was purified by column chromatography to give a cyan powder (231 mg, 68%). Melting point 244.2-246.6 deg.c. ¹ H NMR(400MHz，Chloroform-d)δppm 7.67(m，2H)，7.57(t，1H)，7.29(m，2H) 7.00(dd，J＝8.0，1.6Hz，1H)，6.90(dd，J＝8.4，1.6Hz，1H)，6.87(d，J＝1.6Hz，1H)， 6.70(d，J＝8.0Hz，1H)，6.07(d，J＝1.6Hz，1H)，5.89(d，J＝8.4Hz，1H). ¹³ C NMR (100MHz，Chloroform-d)δppm 147.52，143.49，137.95，136.59，134.43，132.45， 130.52，130.14，129.92，128.06，118.98，118.91，118.82，117.02，116.81(d，2C)， 114.08，107.89，104.94.HRMS(ESI)m/z：[M+H] ⁺ calcd for C ₂₀ H ₁₁ N ₃ O 309.0902， found 309.0909.

Example 5

Preparation of a phenoxazine covalent triazine framework material:

0.25mmol of 2, 7-dicyano-10-methylphenoxazine and 0.5mmol of zinc chloride are added into a 10mL ampoule bottle, then the ampoule bottle is sintered and sealed under vacuum, the reaction mixture is heated to 450 ℃ in a programmed high-temperature oven at 3 ℃/min, and the temperature is kept for 48 hours, and then the temperature is naturally reduced. After the reaction was completed, the obtained solid was ground into powder, and then washed and filtered with 1mol/L hydrochloric acid solution, pure water and tetrahydrofuran, dichloromethane, respectively, in this order, and vacuum-dried at 120℃for 12 hours to obtain black powder with a yield of 60%.

The phenoxazine covalent triazine frame material obtained in the embodiment 5 of the invention is subjected to Fourier infrared, X-ray powder diffraction and nitrogen adsorption tests, and the structure, the crystallinity, the specific surface area and the pore size distribution of the phenoxazine covalent triazine frame material are respectively characterized, and the characterization results are shown in figures 7-9;

as shown in fig. 7, the infrared spectrum of the resulting phenoxazine covalent triazine framework material, the result shows that the cyano (c≡n) characteristic peak in 2, 7-dicyano-10-methylphenoxazine disappears, and a triazine (c=n) bond is formed, demonstrating the successful preparation of the phenoxazine covalent triazine framework material;

As shown in fig. 8, the powder X-ray diffraction pattern of the resulting phenoxazine covalent triazine framework material, the material synthesized by the ionothermal method, appears amorphous;

as shown in FIG. 9, the obtained nitrogen adsorption desorption isothermal diagram of the phenoxazine covalent triazine frame material shows that the prepared phenoxazine covalent triazine frame material has a porous structure and the specific surface area is 1131 and 1131 m ² /g。

Example 6

Preparation of phenothiazine covalent triazine framework materials:

0.25mmol of 2, 7-dicyano-10-methylphenothiazine and 1.25mmol of zinc chloride are added into a 10mL ampoule bottle, then the ampoule bottle is sintered and sealed under vacuum, the reaction mixture is heated to 350 ℃ in a programmed high-temperature oven at 3 ℃/min, and the temperature is kept for 48 hours, and then the temperature is naturally reduced. After the reaction was completed, the obtained solid was ground into powder, and then washed and filtered with 1mol/L hydrochloric acid solution, pure water and tetrahydrofuran, dichloromethane, respectively, in this order, and vacuum-dried at 120℃for 12 hours to obtain black powder with a yield of 55%.

The phenothiazine covalent triazine frame material obtained in the embodiment 6 of the invention is subjected to Fourier infrared, X-ray powder diffraction and nitrogen adsorption tests, and the structure, the crystallinity, the specific surface area and the pore size distribution of the phenothiazine covalent triazine frame material are respectively characterized, and the characterization results are shown in figures 7-9;

As shown in fig. 7, the infrared spectrum of the obtained phenothiazine covalent triazine frame material, the result shows that the characteristic peak of cyano group (c≡n) in 2, 7-dicyano-10-methylphenothiazine disappears, and triazine (c=n) bond is formed, thus proving successful preparation of the phenothiazine covalent triazine frame material;

as shown in fig. 8, the powder X-ray diffraction pattern of the resulting phenothiazine-covalent triazine framework material, the material synthesized by the ionothermal method, exhibited an amorphous shape;

as shown in FIG. 9, the obtained nitrogen adsorption desorption isotherm diagram of the phenothiazine covalent triazine frame material shows that the prepared phenothiazine covalent triazine frame material has a porous structure and the specific surface area is 14m ² /g。

Example 7

Preparation of a lithium ion battery pole piece containing the phenoxazine or phenothiazine covalent triazine frame material:

18mg of the phenoxazine or phenothiazine covalent triazine frame material prepared in the examples 5 and 6 are weighed respectively, ball-milled for 0.5 hour in a ball mill, taken out, 9mg of acetylene black, 120mg of PVDF (PVDF with the concentration of 2.5wt% in N-methylpyrrolidone) binder and a certain amount of N-methylpyrrolidone (NMP) are added for size mixing, the mixture is put into the ball mill for ball milling for 2 hours and uniformly mixed, then a sample uniformly mixed in a ball milling container is coated on a current collector aluminum foil to form a film with the thickness of 200 mu m, the film is dried at 80 ℃ for 12 hours, and the dried electrode film is cut into round electrode plates with the diameter of 14mm, so that the lithium ion battery electrode plate of the phenoxazine or phenothiazine covalent triazine frame material is obtained.

Example 8

Lithium ion battery assembly comprising the phenoxazine or phenothiazine covalent triazine framework material lithium ion battery pole piece:

the lithium-ion battery electrode sheet prepared in example 7 was used as the positive electrode, the metallic lithium sheet was used as the negative electrode, the polypropylene microporous membrane (Celgard 2400) was used as the separator, and 1mol/L LiPF was used ₆ As electrolytes, ethylene Carbonate (EC) and dimethyl carbonate (DMC) (EC/dmc=1:1 v/v) were dissolved, and assembled in a glove box filled with argon gas, and assembled into a coin-type cell of 2016 type.

Characterization of the properties:

the button cell comprising the phenoxazine or phenothiazine covalent triazine framework material obtained in the embodiment 8 is subjected to a cycle stability test, the electrochemical properties of the button cell are characterized, and the characterization results are shown in figures 10-12.

As shown in fig. 10, the cyclic stability test of the prepared phenoxazine and/or phenothiazine covalent organic framework material battery shows that the phenoxazine or phenothiazine covalent triazine framework material has high specific capacity and coulombic efficiency;

as shown in fig. 11, the cyclic voltammogram of the prepared phenoxazine or phenothiazine covalent triazine frame material battery shows that the phenoxazine or phenothiazine covalent triazine frame material shows a certain lithium storage mechanism controlled by pseudo capacitance;

As shown in fig. 12, the electrochemical impedance spectra of the prepared phenoxazine and/or phenothiazine covalent organic framework material cells. The results show that the charge transfer resistances of the phenoxazine and/or phenothiazine covalent organic framework materials are 210 Ω and 310 Ω, respectively, indicating their rapid redox kinetics.

In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.

The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.

Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.

It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.

While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims

1. A phenothiazine or phenoxazine dicyano derivative having a structure represented by formula (ii):

，

Wherein X is selected from O or S, and R is selected from any one of methyl, ethyl, isopropyl and phenyl.

2. The phenothiazine or phenoxazine dicyano derivative according to claim 1, characterized in that it has a structure as shown in formula (iii) or formula (iv):

。

3. a method for producing a phenoxazine dicyano derivative, characterized by comprising:

(1) Reacting a first uniform mixed reaction system containing 4-hydroxy-3-nitrobenzonitrile, a palladium catalyst, a reducing agent and a first solvent for 12-16 hours at 78 ℃ in a protective atmosphere to prepare 4-hydroxy-3-aminobenzonitrile;

(2) Reacting a second uniform mixed reaction system containing the 4-hydroxy-3-aminobenzonitrile, 3, 4-difluorobenzonitrile, a first alkaline substance and a second solvent for 8-12 hours at 100 ℃ in a protective atmosphere to prepare 2, 7-dicyano-10H-phenoxazine;

(3) Reacting a third mixed reaction system comprising the 2, 7-dicyano-10H-phenoxazine, a second alkaline substance, halogenated hydrocarbon and a third solvent for 5-10 hours at 25-35 ℃ to prepare 2, 7-dicyano-10-R-phenoxazine;

the halogenated hydrocarbon is selected from R-X, wherein X is selected from any one of F, cl, br, I, and R is selected from any one of methyl, ethyl, isopropyl and phenyl.

4. A method of preparation according to claim 3, characterized in that: the reducing agent in the step (1) comprises hydrazine hydrate, and the mass concentration of the hydrazine hydrate is 80 wt%.

5. A method of preparation according to claim 3, characterized in that: the first solvent comprises an alcohol solvent and/or a mixed solution of the alcohol solvent and a high-solubility solvent, wherein the alcohol solvent is selected from methanol and/or ethanol, and the high-solubility solvent is selected from ethyl acetate and/or chloroform.

6. A method of preparation according to claim 3, characterized in that: the palladium catalyst comprises a palladium-carbon catalyst; the palladium on carbon catalyst comprises 5 wt% palladium with the remainder comprising activated carbon.

7. The method of claim 3, wherein step (1) further comprises: and after the reaction of the first uniform mixed reaction system is finished, filtering and purifying the obtained mixture.

8. The method of manufacturing according to claim 7, wherein: the purification treatment comprises extraction and column chromatography separation and purification treatment.

9. A method of preparation according to claim 3, characterized in that: the first alkaline substance comprises potassium hydroxide and/or potassium carbonate.

10. A method of preparation according to claim 3, characterized in that: the second solvent comprises dimethyl sulfoxide and/orN,NDimethylformamide.

11. The method of claim 3, wherein step (2) further comprises: and after the reaction of the second uniform mixed reaction system is finished, filtering, washing and purifying the obtained mixture.

12. The method of claim 11, wherein the purification treatment comprises: the collected product was dried, and then washed with ethyl acetate and filtered.

13. A method of preparation according to claim 3, characterized in that: the molar ratio of the 2, 7-dicyano-10H-phenoxazine, the second basic material and the halohydrocarbon in the step (3) is 1:1.5:2.

14. A method of preparation according to claim 3, characterized in that: the second alkaline substance comprises sodium hydride and/or potassium carbonate.

15. A method of preparation according to claim 3, characterized in that: the third solvent comprisesN,NDimethylformamide and/or dimethyl sulfoxide.

16. The method of claim 3, wherein step (3) further comprises: and after the reaction of the third mixed reaction system is finished, washing, drying and purifying the obtained mixture.

17. The method of claim 15, wherein the purification treatment comprises: the product after the drying treatment is washed and filtered by ethyl acetate.

18. A method of preparation according to claim 3, characterized in that: the protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.

19. A method for producing a phenothiazine dicyano derivative, comprising:

(2) Reacting a first mixed reaction system comprising the 2-chloro-7-bromo-10H-phenothiazine, a first alkaline substance, a halogenated hydrocarbon and a first solvent for 1 hour at room temperature in a protective atmosphere to prepare 2-chloro-7-bromo-10-R-phenothiazine;

(3) Reacting a second mixed reaction system containing the 2-chloro-7-bromo-10-R-phenothiazine, cuprous cyanide and a second solvent for 12-24 hours at 140-150 ℃ to prepare 2, 7-dicyano-10-R-phenothiazine;

20. The method of manufacturing according to claim 19, wherein: the molar ratio of the 2, 7-dicyano-10H-phenothiazine, the first basic substance and the halogenated hydrocarbon in the step (2) is 1:1.5:2.

21. The method of manufacturing according to claim 19, wherein: the first solvent comprisesN,NDimethylformamide and/or dimethyl sulfoxide.

22. The method of claim 19, wherein step (2) further comprises: and after the reaction of the first mixed reaction system is finished, washing, drying and purifying the obtained mixture.

23. The method of manufacturing according to claim 19, wherein: the molar ratio of the 2-chloro-7-bromo-10-R-phenothiazine to the cuprous cyanide in the step (3) is 1:2.4.

24. The method of manufacturing according to claim 19, wherein: the second solvent in step (3) comprisesN,N-dimethylformamide and/or N-methylpyrrolidone.

25. The method of claim 19, wherein step (3) further comprises: and after the reaction of the second mixed reaction system is finished, washing, drying and purifying the obtained mixture.

26. The method of claim 25, wherein the purifying treatment comprises: the obtained product was dried and then separated by column chromatography.

27. The method of manufacturing according to claim 19, wherein: the protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.

28. Use of a phenoxazine or phenothiazine dicyano derivative according to claim 1 or 2 for the preparation of a phenoxazine or phenothiazine covalent triazine framework material having a structure according to formula (i):

，

29. A phenoxazine or phenothiazine covalent triazine framework material characterized in that it has a structure according to formula (i):

，

30. A method for preparing a phenoxazine or phenothiazine covalent triazine framework material, comprising: carrying out ion melting reaction on the phenoxazine or phenothiazine dicyano derivative according to claim 1 or 2 and zinc chloride, and washing with water and acid after the reaction is finished, wherein the obtained solid is a phenoxazine or phenothiazine covalent triazine framework material;

wherein the ratio of the amounts of the substances of the phenoxazine or phenothiazine dicyano derivative and zinc chloride is 1: 1-20 parts;

The conditions of the ion melting reaction are as follows: and in a vacuum sealed environment, heating to 350-600 ℃ and reacting for 24-72 hours.

31. The method of manufacturing according to claim 30, wherein: the phenoxazine or phenothiazine dicyano derivative is selected from 2, 7-dicyano-10-methyl phenoxazine and/or 2, 7-dicyano-10-methyl phenothiazine.

32. The method of manufacturing according to claim 30, wherein: the acid solution is hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 1-5 mol/L.

33. The method of manufacturing according to claim 30, further comprising: after washing the obtained reaction product by using water and acid, the reaction product is dried in vacuum for 12-24 hours at 50-100 ℃.

34. Use of a phenoxazine or phenothiazine covalent triazine framework material according to claim 29 in a lithium ion battery cathode material.

35. A positive electrode for a lithium ion battery comprising at least the phenoxazine or phenothiazine covalent triazine framework material of claim 29.

36. A lithium ion battery comprises an anode, a cathode and electrolyte, and is characterized in that: the positive electrode comprising the lithium ion battery positive electrode of claim 35.

37. The preparation method of the lithium ion battery is characterized by comprising the following steps: the phenoxazine or phenothiazine covalent triazine frame material, the conductive agent and the binder according to claim 29 are uniformly mixed, the obtained mixture is applied to a conductive current collector to form a battery anode, and then the battery anode, the negative electrode and the electrolyte are assembled into a lithium ion battery.

38. The method of manufacturing according to claim 37, wherein: the conductive current collector comprises an unclamped aluminum foil and/or a carbon-coated aluminum foil.

39. The method of manufacturing according to claim 37, wherein: the lithium ion battery comprises a button battery.