CN113512033A - Phenoxazine and phenothiazine covalent triazine framework material and preparation method and application thereof - Google Patents
Phenoxazine and phenothiazine covalent triazine framework material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113512033A CN113512033A CN202110550453.1A CN202110550453A CN113512033A CN 113512033 A CN113512033 A CN 113512033A CN 202110550453 A CN202110550453 A CN 202110550453A CN 113512033 A CN113512033 A CN 113512033A
- Authority
- CN
- China
- Prior art keywords
- phenothiazine
- phenoxazine
- dicyano
- framework material
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229950000688 phenothiazine Drugs 0.000 title claims abstract description 105
- 239000000463 material Substances 0.000 title claims abstract description 95
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 title claims abstract description 91
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000013311 covalent triazine framework Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 32
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
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- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 239000011592 zinc chloride Substances 0.000 claims abstract description 12
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- 150000002500 ions Chemical class 0.000 claims abstract description 6
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- -1 2-chloro-7-bromo-10H-phenothiazine Chemical compound 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- CUCILOOMNYZYOA-UHFFFAOYSA-N 10H-phenoxazine-2,7-dicarbonitrile Chemical compound C1=CC2=C(C=C1C#N)OC3=C(N2)C=C(C=C3)C#N CUCILOOMNYZYOA-UHFFFAOYSA-N 0.000 claims description 21
- ZEWCASRNRWXXSO-UHFFFAOYSA-N 3-amino-4-hydroxybenzonitrile Chemical compound NC1=CC(C#N)=CC=C1O ZEWCASRNRWXXSO-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
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- BTBFCBQZFMQBNT-UHFFFAOYSA-N 3,4-difluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1F BTBFCBQZFMQBNT-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
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- ADKJUYJDPFVFFI-UHFFFAOYSA-N CN1C(C=C(C=C2)C#N)=C2OC2=CC(C#N)=CC=C12 Chemical group CN1C(C=C(C=C2)C#N)=C2OC2=CC(C#N)=CC=C12 ADKJUYJDPFVFFI-UHFFFAOYSA-N 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 7
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- KFZGLJSYQXZIGP-UHFFFAOYSA-N 2-chloro-10h-phenothiazine Chemical compound C1=CC=C2NC3=CC(Cl)=CC=C3SC2=C1 KFZGLJSYQXZIGP-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011530 conductive current collector Substances 0.000 claims description 5
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/38—[b, e]-condensed with two six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a phenoxazine or phenothiazine covalent triazine framework material, a preparation method and application thereof. The phenoxazine or phenothiazine covalent triazine framework material is prepared by the following method: the phenoxazine or phenothiazine dicyano derivative is adopted to carry out ion melting reaction with zinc chloride, after the reaction is finished, water and acid are used for washing, and the obtained solid product is the phenoxazineOxazine or phenothiazine covalent triazine framework materials. The structure of the phenoxazine or phenothiazine covalent triazine framework material is shown as the following formula (I):
the phenoxazine or phenothiazine covalent triazine framework material prepared by 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 rate capability and the like, and has good application prospect in novel high-performance organic electrode materials.
Description
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 phenoxazine or phenothiazine covalent triazine framework material, and a preparation method and application thereof. The application is the application of a phenoxazine or phenothiazine covalent triazine framework material in the energy related field, and particularly relates to the synthesis of a phenoxazine or phenothiazine dicyano derivative and a phenoxazine or phenothiazine covalent triazine framework material and the application of the phenoxazine or phenothiazine covalent triazine framework material in a lithium ion battery anode material.
Background
As a rechargeable secondary battery, a lithium ion battery has been successfully applied to various energy storage fields since its development because of its advantages of high energy and power density, long service life, and the like. The positive electrode material is an important factor for restricting the increase of the energy density of the battery. Compared with the traditional cathode material (transition metal oxide), the organic cathode material (comprising carbonyl compound, conductive polymer, free radical compound and the like) is widely applied to the cathode material of the lithium ion battery due to the characteristics of easily available raw materials, various structures, environmental friendliness and the like. However, the conventional organic materials have limited applications due to their disadvantages of poor conductivity, low redox potential, and dissolution in organic electrolytes.
The covalent triazine framework material is a porous material with good chemical stability and thermal stability, and the framework of the material contains rich nitrogen elements, so that the surface of the material has polarity, and the covalent triazine framework material has huge practical application prospects in the fields of gas adsorption separation, heterogeneous catalysis, photoelectric technology and the like. Diheteroanthracene derivatives are aromatic heterocyclic structures containing an electron-rich nitrogen atom and an oxygen (or sulfur) atom, which are susceptible to losing one electron to form radical cations. The covalent triazine framework material is used as the anode material of the lithium ion battery, the N-type covalent triazine framework material has higher theoretical specific capacity, but the actual capacity is lower because the steric hindrance of the grain boundary is large, the intrinsic conductivity is low, the actual utilization of active sites is limited; when the diheteroanthracene-based micromolecules or polymers are used as the battery anode material, typical P-type materials are represented, and the diheteroanthracene-based micromolecules or polymers have the advantages of high voltage, high cycling stability and the like when being used as the battery anode material, but the theoretical specific capacity is lower. Therefore, the design of the P-N composite novel diheteroanthracene (also called phenoxazine or phenothiazine) covalent triazine framework material applied to the battery anode material has important significance and extremely challenges.
Disclosure of Invention
Aiming at the defects in the prior art, the invention mainly aims to provide a phenoxazine or phenothiazine dicyano derivative and a preparation method thereof, and a phenoxazine or phenothiazine covalent triazine framework material and a preparation method and application thereof.
In order to achieve the purpose, 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 in a formula (II):
wherein, X is selected from O or S, and R is selected from any one of linear alkyl, branched alkyl and aromatic ring group. 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 at 78 ℃ for 12-16 hours under a protective atmosphere to prepare 4-hydroxy-3-aminobenzonitrile;
(2) reacting a second uniformly mixed reaction system containing the 4-hydroxy-3-aminobenzonitrile, the 3, 4-difluorobenzonitrile, the first alkaline substance and the second solvent at 100 ℃ for 8-12 hours under a protective atmosphere to obtain 2, 7-dicyano-10H-phenoxazine;
(3) and reacting a third mixed reaction system containing the 2, 7-dicyano-10H-phenoxazine, a second basic substance, halogenated hydrocarbon and a third solvent at 25-35 ℃ for 5-10 hours to obtain 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-chloro-phenothiazine, liquid bromine and acetic acid at room temperature for 24 hours under a protective atmosphere to prepare 2-chloro-7-bromo-10H-phenothiazine;
(2) and reacting the first mixed reaction system containing the 2-chloro-7-bromo-10H-phenothiazine, the first alkaline substance, the halogenated hydrocarbon and the first solvent at room temperature for 1 hour under 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 at 140-150 ℃ for 12-24 hours to obtain the 2, 7-dicyano-10-R-phenothiazine.
The embodiment of the invention also provides a phenoxazine or phenothiazine covalent triazine framework material, which has a structure shown in a formula (I):
the embodiment of the invention also provides a preparation method of the covalent triazine framework material based on the phenoxazine or the phenothiazine, which comprises the following steps:
the mass 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: and (3) in a vacuum closed environment, raising the temperature to 350-600 ℃ by a program, and reacting for 24-72 hours.
The embodiment of the invention also provides application of the phenoxazine or phenothiazine covalent triazine framework material in a lithium ion battery cathode material.
The embodiment of the invention also provides a lithium ion battery anode, which at least comprises the phenoxazine or phenothiazine covalent triazine framework material.
The embodiment of the invention also provides a lithium ion battery, which comprises an anode, a cathode and electrolyte, wherein the anode comprises the lithium ion battery anode.
The embodiment of the invention also provides a preparation method of the lithium ion battery, which comprises the following steps:
uniformly mixing the phenoxazine or phenothiazine covalent triazine framework material, a conductive agent and a binder, then applying the obtained mixture on a conductive current collector to form a battery anode, and then assembling the battery anode, a cathode 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 uses commercial 4-hydroxy-3-nitrobenzonitrile as a raw material, intramolecular nitro reduction is firstly carried out, then nucleophilic substitution reaction of intermolecular aryl is carried out on the intramolecular nitro reduction and 3, 4-difluorobenzonitrile under an alkaline condition, and then the intramolecular nucleophilic substitution reaction is carried out to close the ring to obtain the 2, 7-dicyano-10-R-phenoxazine. Commercial 2-chlorophenothiazine is used as a raw material, bromination is carried out firstly, then methyl is carried out, and finally, cyanide replaces halogen to obtain the 2, 7-dicyano-10-R-phenothiazine. And carrying out cyano trimerization on the obtained 2, 7-dicyano-10-R-phenoxazine and/or 2, 7-dicyano-10-R-phenothiazine under the condition of melting zinc chloride to obtain the phenoxazine or phenothiazine covalent triazine framework material. The reaction process of the 2, 7-dicyano-10-R-phenoxazine/phenothiazine prepared by the invention is simple to operate, the synthetic route is simple, and the reaction yield is high, and the compound provides an important synthetic precursor for the covalent triazine framework material; the covalent triazine framework material based on the phenoxazine or the phenothiazine has high specific surface area, good thermal stability and high oxidation-reduction potential (3.5V vs. Li/Li)+) And multiple pairs of redox peaks, so that the phenoxazine or phenothiazine covalent triazine framework material prepared by the invention can be applied to a lithium ion battery anode material, and has a 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 needed to be 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 described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a nuclear magnetic hydrogen spectrum of 3-amino-4-hydroxybenzonitrile produced in step (1) of example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 2, 7-dicyano-10H-phenoxazine prepared in step (2) in example 1 of the present invention;
FIG. 3 is a nuclear magnetic 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 hydrogen spectrum of 2-chloro-7-bromo-10H-phenothiazine produced in step (1) in example 2 of the present invention;
FIG. 5 is a nuclear magnetic hydrogen spectrum of 2-chloro-7-bromo-10-methyl-phenothiazine produced in step (2) in example 2 of the present invention;
FIG. 6 is a nuclear magnetic hydrogen spectrum of 2, 7-dicyano-10-methylphenothiazine prepared in step (3) of example 2 of the present invention;
FIG. 7 is an IR 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 a phenoxazine or phenothiazine covalent triazine framework material obtained in example 3 of the present invention;
FIG. 9 is a plot of the nitrogen adsorption desorption isotherm of the phenoxazine or phenothiazine covalent triazine framework material obtained in example 3 of the present invention.
FIG. 10 is a graph showing the cycling stability 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 cycled for 100 circles, the discharge specific capacity can still be respectively maintained at 159mAh/g and 126mAh/g, and the capacity retention rates are respectively 82% and 92% (after the phenoxazine and/or phenothiazine covalent organic framework material is cycled for 10 circles, the initial discharge specific capacity is respectively 192mAh/g and 136 mAh/g).
FIG. 11 shows the cycle voltage of phenoxazine or phenothiazine covalent triazine framework cells in example 8 of the inventionAmpere graph. The phenoxazine covalent triazine framework material shows a certain pseudocapacitance lithium storage mechanism, and the phenothiazine covalent triazine framework material shows three pairs of oxidation-reduction peaks which are respectively E of triazine ringO1/R12.3/2.5V, E of phenothiazine first potentialO2/R23.6/3.5V and phenothiazine second potential EO3/R3～4.2/4.3V。
FIG. 12 is the electrochemical impedance spectrum of the phenoxazine and/or phenothiazine covalent organic framework material cell in example 8 of the present invention. The charge transfer resistance of the phenoxazine and/or phenothiazine covalent organic framework material is 210 Ω and 310 Ω, respectively.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of an embodiment of the present invention provides a phenoxazine or phenothiazine 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 linear alkyl, branched alkyl and aromatic ring group.
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 linear alkyl, branched alkyl and aromatic ring group, 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):
wherein R is selected from any one of linear alkyl, branched alkyl and aromatic ring group, preferably any one of methyl, ethyl, isopropyl, phenyl and naphthyl.
An aspect of an embodiment of the present invention further provides a phenoxazine or phenothiazine covalent triazine framework material, which has a structure represented by formula (I):
in some more specific embodiments, the phenoxazine covalent triazine framework material has a specific surface area of 1131m2(ii)/g, pore diameter 1.29 nm; phenothiazine covalent triazine framework material with a specific surface area of 14m2Per g, pore size 4.22 nm.
In the invention, the phenoxazine covalent triazine framework material with the structure shown in the formula (I) is named DCPO-CTF (X ═ O, R ═ CH)3.); phenothiazine covalent triazine frame material is named DCPT-CTF (X ═ S, R ═ CH)3)。
Another aspect of an embodiment of the present invention also provides a method for preparing a phenoxazine dicyano derivative, which includes:
(1) reacting a first uniformly mixed reaction system containing 4-hydroxy-3-nitrobenzonitrile, a palladium catalyst, a reducing agent and a first solvent at 78 ℃ for 12-16 hours under a protective atmosphere to prepare 4-hydroxy-3-aminobenzonitrile;
(2) reacting a second uniformly mixed reaction system containing the 4-hydroxy-3-aminobenzonitrile, the 3, 4-difluorobenzonitrile, the first alkaline substance and the second solvent at 100 ℃ for 8-12 hours under a protective atmosphere to obtain 2, 7-dicyano-10H-phenoxazine;
(3) and reacting a third mixed reaction system containing the 2, 7-dicyano-10H-phenoxazine, a second basic substance, halogenated hydrocarbon and a third solvent at 25-35 ℃ for 5-10 hours to obtain the phenoxazine dinitrile derivative.
In some specific embodiments, the molar ratio of the palladium catalyst to the reducing agent in the 4-hydroxy-3-nitrobenzonitrile in step (1) is 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 80 wt%.
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 of methanol and ethanol or a combination of both, and is not limited thereto.
Further, the high-solubility solvent includes any one or a combination of two of ethyl acetate or 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 comprises: palladium 5 wt%, the remainder comprising activated carbon.
In some more specific embodiments, the preparation method 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 and the first basic substance in step (2) is 1: 1.5 to 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 preparation method further comprises: and after the reaction of the first uniformly mixed reaction system is finished, washing, drying and purifying the obtained mixture.
Further, the purification treatment comprises: and stirring the dried product in ethyl acetate for about 5min, and filtering the obtained solid product.
In some more specific embodiments, the molar ratio of the 2, 7-dicyano-10H-phenoxazine, the second basic material, and the 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, and I, and R is selected from any one of a linear alkyl group, a branched alkyl group, and an aromatic ring group, and preferably, R is selected from any one of a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a naphthyl group, without being limited thereto.
Further, the second basic 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 for preparing the phenoxazine dicyano derivative comprises:
(1) dissolving 4-hydroxy-3-nitrobenzonitrile in alcohol solvent, adding solid palladium catalyst, using hydrazine hydrate as reducing agent, refluxing at 78 deg.C for 12 hr. After the reaction is finished, filtering the system by using diatomite, spin-drying the filtrate, adding water, extracting by using ethyl acetate, collecting an organic phase, and finally purifying by using column chromatography to obtain the 4-hydroxy-3-aminobenzonitrile.
(2) Dissolving 4-hydroxy-3-aminobenzonitrile, 3, 4-difluorobenzonitrile and potassium hydroxide in dimethyl sulfoxide, heating to 100 ℃, after the reaction is finished, adding water into the system for treatment, filtering to obtain a solid, drying, stirring in ethyl acetate, and filtering to obtain the solid which is the intermediate product 2, 7-dicyano-10H-phenoxazine.
(3) Reacting 2, 7-dicyano-10H-phenoxazine, sodium hydride, halohydrocarbon (R-X) and N, N-dimethylformamide under the protection of nitrogen, adding water into the system for treatment after the reaction is finished, and filtering to obtain the 2, 7-dicyano-10-R-phenoxazine.
Preferably, in the step (1), the alcohol solvent is methanol or ethanol or a mixed solution of an alcohol and a high-solubility solvent.
Further, in the step (1), the solid palladium catalyst adopts palladium carbon, wherein the palladium carbon comprises 5 wt% of palladium, and the rest part comprises activated 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, the 3, 4-difluorobenzonitrile and the first alkaline substance is 1: 1.5-1: 2.5.
Further, in the step (3), the molar ratio of the 2, 7-dicyano-10H-phenoxazine to the second basic substance to the halogenated hydrocarbon is 1: 1.5: 2.
In another aspect of the embodiments of the present invention, there is provided a method for preparing a phenothiazine dicyano derivative, including:
(1) reacting a uniformly mixed reaction system containing 2-chloro-phenothiazine, liquid bromine and acetic acid at room temperature for 24 hours under a protective atmosphere to prepare 2-chloro-7-bromo-10H-phenothiazine;
(2) and reacting the first mixed reaction system containing the 2-chloro-7-bromo-10H-phenothiazine, the first alkaline substance, the halogenated hydrocarbon and the first solvent at room temperature for 1 hour under 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 at 140-150 ℃ for 12-24 hours to obtain the 2, 7-dicyano-10-R-phenothiazine.
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 halogenated hydrocarbon includes R — X, wherein X is selected from any one of F, Cl, Br, and I, and R is selected from any one of a linear alkyl group, a branched alkyl group, and an aromatic ring group, and preferably, R is selected from any one of a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a naphthyl group, without being limited thereto.
Further, the first basic 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.
Further, the protective atmosphere includes a nitrogen atmosphere or an argon atmosphere, 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 includes 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 uniformly mixed reaction system is finished, washing, drying and purifying the obtained mixture; preferably the purification treatment comprises: separating the dried product by column chromatography.
In another aspect, the embodiments of the present invention further provide a method for preparing a phenoxazine or phenothiazine covalent triazine framework material, which includes:
the mass 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: and (3) heating to 350-600 ℃ in a vacuum closed environment, and reacting 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-methylphenthiazine.
Further, the mass ratio of the 2, 7-dicyano-10-methylphenoxazine and/or the 2, 7-dicyano-10-methylphenthiazine to the zinc chloride is 1: 1-20.
In some more specific embodiments, the preparation method further comprises: after the reaction is completed, the obtained mixture is filtered, washed and dried.
Further, the washing liquid used in the washing treatment comprises acid, distilled water and organic solvent.
Further, the acid solution is a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 1-5 mol/L.
Further, the organic solvent is selected from tetrahydrofuran and 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 the phenoxazine or phenothiazine covalent triazine framework material comprises:
(1) sealing 2, 7-dicyano-10-methylphenoxazine and/or 2, 7-dicyano-10-methylphenothiazine and zinc chloride in a vacuum state;
(2) and (2) placing the mixed system prepared in the step (1) in a high-temperature program oven, heating to 450 ℃ from room temperature at the speed of 3 ℃/min, preserving the heat for 48 hours, and then naturally cooling to room temperature.
(3) After the heating reaction is finished, after the reaction container is cooled to room temperature, collecting black solid products, respectively and sequentially filtering and washing the black solid products by hydrochloric acid, tetrahydrofuran and dichloromethane, and then drying the black solid products in vacuum to finally obtain the covalent triazine framework material.
Further, the mass ratio of the 2, 7-dicyano-10-methylphenoxazine and/or the 2, 7-dicyano-10-methylphenthiazine to the zinc chloride in the step (1) is 1: 1-20.
Further, the temperature in step (2) is 450 ℃, but not limited thereto.
Further, the concentration of the hydrochloric acid solution in the step (3) is 1mol/L, but 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 method of making can comprise: under the condition of ionothermal, putting the mixed system of the 2, 7-dicyano-10-methylphenoxazine and/or the 2, 7-dicyano-10-methylphenazinium and zinc chloride into a 10mL ampoule bottle, sealing the ampoule bottle under the vacuum state, putting the ampoule bottle into a high-temperature programmed heating oven, heating the ampoule bottle to 450 ℃, maintaining the temperature for 48 hours, naturally cooling the ampoule bottle, collecting black solids, filtering and washing the black solids by using hydrochloric acid, tetrahydrofuran and dichloromethane, and drying the black solids in vacuum for 12 hours at 120 ℃ to obtain black solids, namely the covalent triazine framework material of the phenoxazine or phenothiazine.
Yet another aspect of an embodiment of the present invention provides a phenoxazine or phenothiazine covalent triazine framework material prepared by the foregoing method.
Another aspect of the embodiments of the present invention also provides a use of the aforementioned phenoxazine or phenothiazine covalent triazine framework material in a positive electrode of a lithium ion battery.
In the invention, the phenoxazine or phenothiazine covalent triazine framework material has redox activity when being used for the research of the anode of the lithium ion battery.
Another aspect of the embodiments of the present invention also provides a lithium ion battery positive electrode, which at least includes the aforementioned phenoxazine or phenothiazine covalent triazine framework material.
Another aspect of the embodiment of the present invention further provides a lithium ion battery, including a positive electrode, a negative electrode, and an electrolyte, where the positive electrode includes the positive electrode of the lithium ion battery.
Another aspect of the embodiments of the present invention also provides a method for preparing a lithium ion battery, including: uniformly mixing the phenoxazine or phenothiazine covalent triazine frame material, a conductive agent and a binder, then applying the obtained mixture on a conductive current collector to form a battery anode, and then assembling the battery anode, a cathode and an electrolyte into a 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 used as raw materials, and the reaction route for synthesizing phenoxazine or phenothiazine dicyano derivative is as follows:
the technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Synthesis of 3-amino-4-hydroxybenzonitrile:
4-hydroxy-3-nitrobenzonitrile (20mmol, 3.28g), palladium on carbon (55% water) (2mmol, 472mg) were weighed accurately into a 250mL pre-dried three-necked round bottom flask. Under nitrogen atmosphere, 100mL of oxygen-free ethanol was added with stirring. After the system was dissolved, hydrazine hydrate (85 wt%) (200mmol, 11.12mL) was added dropwise to the system and refluxed at 78 ℃ for 12 hours. After the reaction was complete, the reaction was cooled to room temperature, the system was filtered through celite to obtain a filtrate, the filtrate was spin-dried, 20mL of water was added, the organic phase was collected by extraction with ethyl acetate (3 × 20mL), and spin-dried. Separating and purifying by column chromatography to obtain 2.15g of 3-amino-4-hydroxybenzonitrile with 80% yield. The hydrogen spectrum of nuclear magnetic resonance is shown in figure 1,1H NMR(400MHz，DMSO-d6)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 (20mmol, 2.68g), 3, 4-difluorobenzonitrile (20mmol, 2.78g), and potassium hydroxide (40mmol, 2.24g) were accurately weighed into a 250mL three-necked flask, 100mL of dimethyl sulfoxide solvent 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 separating out 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 obtain 3.5g of the product 2, 7-dicyano-10H-phenoxazine in 75% yield. The melting point is 300.2-300.4 ℃. The hydrogen spectrum of nuclear magnetic resonance is shown in figure 2,1H NMR(400MHz，DMSO-d6)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).13C NMR(100MHz，DMSO-d6)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 C14H7N3O 234.0667；found 234.0659.
(3) synthesis of 2, 7-dicyano-10-methylphenoxazine
Taking 2, 7-dicyano-10H-phenoxazine (10mmol, 2.33g) and sodium hydride (15mmol, 300mg) in a 250mL three-neck round-bottom flask, adding an ultra-dry solvent N, N-dioxazine into the flask under nitrogen atmosphere and stirringAfter the system was dissolved, methyl iodide (20mmol, 1.24mL) was slowly added dropwise and the reaction was allowed to proceed overnight at room temperature. After the reaction is finished, 50mL of water is added and stirred, a large amount of brown solid is separated out from the system, filtered, and a filter cake is collected and dried in vacuum. The drained product was then dissolved in ethyl acetate, filtered and washed several times with ethyl acetate to give 1.73g of a grayish-blue product in 70% yield. The melting point is 278-279 ℃. The hydrogen spectrum of nuclear magnetic resonance is shown in figure 3,1H NMR(400MHz，DMSO-d6)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).13C NMR(100MHz，DMSO-d6)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 C15H9N3O 248.0824，found 248.0819.
example 2
(1) Synthesis of 2-chloro-7-bromo-10H-phenothiazine
2-Chlorothiazine (5mmol, 1.18g) was accurately weighed into a 100mL two-necked round bottom flask, and 25mL of oxygen-free CH was added under nitrogen3COOH, dropping Br into the solution at constant pressure while stirring2(0.24mL in 25mL CH3COOH), reaction for 24 hours. Adding Na into the system after the reaction of the system is finished2S2SO3Stirring the solution, adding NaOH solution, stirring, filtering, washing the filter cake with water, washing with cold isopropanol, collecting the filter cake, and drying. Recrystallization from toluene was repeated several times to give a silvery white solid (1g, 64%). The hydrogen spectrum of nuclear magnetic resonance is shown in FIG. 41H NMR(400MHz，DMSO-d6)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 (155.46mg, 0.5mmol) was weighed accurately into a 10mL two-necked flask, 5mL of ultra-dry N, N-dimethylformamide was added under nitrogen, sodium hydride (30mg, 0.75mmol) was added after the raw material had dissolved, methyl iodide (1mmol, 0.062mL) was added with stirring for half an hour, and stirring was carried out at room temperature for 1 hour. After the reaction is finished, adding water, stirring, filtering, washing a filter cake, collecting the filter cake and drying. A pale pink solid was obtained (130 mg, 80%). The hydrogen spectrum of nuclear magnetic resonance is shown in figure 5,1H NMR(400MHz，DMSO-d6)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 (1.5mmol, 487.4mg) and cuprous cyanide (2.4mmol, 322.4mg) were weighed accurately into a pre-dried three-necked 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. A cyan powder (250mg, 63%) was obtained. The melting point is 204-206 ℃. The hydrogen spectrum of nuclear magnetic resonance is shown in figure 6,1H NMR(400MHz，DMSO-d6)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).13C 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 C15H9N3S 264.0595，found 264.0578.
example 3
(1) Synthesis of 3-amino-4-hydroxybenzonitrile:
4-hydroxy-3-nitrobenzonitrile (20mmol, 3.28g), palladium on carbon (55% water) (2mmol, 472mg) were weighed accurately into a 250mL pre-dried three-necked round bottom flask. Under nitrogen atmosphere, 100mL of oxygen-free ethanol was added with stirring. After the system was dissolved, hydrazine hydrate (85 wt%) (200mmol, 11.12mL) was added dropwise to the system and refluxed at 78 ℃ for 12 hours. After the reaction was complete, the reaction was cooled to room temperature, the system was filtered through celite to obtain a filtrate, the filtrate was spin-dried, 20mL of water was added, the organic phase was collected by extraction with ethyl acetate (3 × 20mL), and spin-dried. Separation and purification by column chromatography gave 2.15g of 3-amino-4-hydroxybenzonitrile with a yield of 80%. The hydrogen spectrum of nuclear magnetic resonance is shown in figure 1,1H NMR(400MHz，DMSO-d6)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 (20mmol, 2.68g), 3, 4-difluorobenzonitrile (20mmol, 2.78g), and potassium hydroxide (40mmol, 2.24g) were accurately weighed into a 250mL three-necked flask, 100mL of dimethyl sulfoxide solvent 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 separating out 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 obtain 3.5g of 2, 7-dicyano-10H-phenoxazine as a product in a 75% yield. The melting point is 300.2-300.4 ℃. The hydrogen spectrum of nuclear magnetic resonance is shown in figure 2,1H NMR(400MHz，DMSO-d6)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).13C NMR(100MHz，DMSO-d6)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 C14H7N3O 234.0667；found 234.0659.
(3) synthesis of 2, 7-dicyano-10-butylphenoxazine
2, 7-dicyano-10H-phenoxazine (116.5mg, 0.5mmol) and sodium hydroxide (168mg, 4.2 mmol) were taken in a 10mL round bottom flask, solvent dimethylsulfoxide (5mL) was added under nitrogen, 1-bromobutane (0.1mL, 0.85mmol) was added slowly and stirred at room temperature for 24H. 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 (100mg, 69%). The melting point is 220.3-222.3 ℃.1H 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).13C 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 C18H15N3O 290.1293，found 290.1292.
Example 4
(1) Synthesis of 3-amino-4-hydroxybenzonitrile:
4-hydroxy-3-nitrobenzonitrile (20mmol, 3.28g), palladium on carbon (55% water) (2mmol, 472mg) were weighed accurately into a 250mL pre-dried three-necked round bottom flask. Under nitrogen atmosphere, 100mL of oxygen-free ethanol was added with stirring. After the system was dissolved, hydrazine hydrate (85 wt%) (200mmol, 11.12mL) was added dropwise to the system and refluxed at 78 ℃ for 12 hours. After the reaction was complete, the reaction was cooled to room temperature, the system was filtered through celite to obtain a filtrate, the filtrate was spin-dried, 20mL of water was added, the organic phase was collected by extraction with ethyl acetate (3 × 20mL), and spin-dried. Separation and purification by column chromatography gave 2.15g of 3-amino-4-hydroxybenzonitrile with a yield of 80%. The hydrogen spectrum of nuclear magnetic resonance is shown in figure 1,1H NMR(400MHz，DMSO-d6)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 (20mmol, 2.68g), 3, 4-difluorobenzonitrile (20mmol, 2.78g), and potassium hydroxide (40mmol, 2.24g) were accurately weighed into a 250mL three-necked flask, 100mL of dimethyl sulfoxide solvent 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 separating out 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 obtain 3.5g of the product 2, 7-dicyano-10H-phenoxazine in 75% yield. The melting point is 300.2-300.4 ℃. The hydrogen spectrum of nuclear magnetic resonance is shown in figure 2,1H NMR(400MHz，DMSO-d6)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).13C NMR(100MHz，DMSO-d6)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 C14H7N3O 234.0667；found 234.0659.
(3) synthesis of 2, 7-dicyano-10-butylphenoxazine
Taking 2, 7-dicyano-10H-phenoxazine (256.3mg, 1.10mmol), bromobenzene (0.11mL, 1.00mmol), Pd (dba)2(35mg, 6 mol%), tri-tert-butylphosphine tetrafluoroborate (17mg, 6 mol%) and sodium tert-butoxide (111mg, 1.15mmol) were dissolved in dry 1, 4-dioxane (3 mL). The system was degassed under nitrogen for 5 minutes. Then, the reaction mixture was stirred at 100 ℃ for 14 hours. After cooling to room temperature, deionized water (50mL), saturated Na were added in sequence2SO3Solution (15mL) and dichloromethane (50 mL). The aqueous phase was extracted with dichloromethane (3 x 10 mL). 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 (231mg, 68%). The melting point is 244.2-246.6 ℃.1H 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).13C 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 C20H11N3O 309.0902， found 309.0909.
Example 5
Preparation of phenoxazine covalent triazine framework material:
adding 0.25mmol of 2, 7-dicyano-10-methylphenoxazine and 0.5mmol of zinc chloride into a 10mL ampoule bottle, sintering and sealing the ampoule bottle under the vacuum condition, heating the reaction mixture to 450 ℃ at the speed of 3 ℃/min in a programmed high-temperature oven, preserving the temperature for 48 hours, and then naturally cooling. 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, tetrahydrofuran, and dichloromethane, respectively, and dried under vacuum at 120 ℃ for 12 hours to obtain black powder with a yield of 60%.
Fourier infrared and X-ray powder diffraction and nitrogen adsorption tests are carried out on the phenoxazine covalent triazine framework material obtained in the embodiment 5 of the invention, the structure, the crystallinity, the specific surface area and the pore size distribution are respectively characterized, and the characterization result is shown in figures 7-9;
as shown in fig. 7, the infrared spectrum of the obtained phenoxazine covalent triazine framework material shows that characteristic peak of cyano (C ≡ N) in 2, 7-dicyano-10-methylphenoxazine disappears, and triazine (C ≡ N) bond is formed at the same time, thus proving successful preparation of phenoxazine covalent triazine framework material;
as shown in fig. 8, the powder X-ray diffraction pattern of the obtained phenoxazine covalent triazine framework material, the material synthesized by the ionothermal method appeared amorphous;
as shown in FIG. 9, the nitrogen adsorption and desorption isotherm diagram of the obtained phenoxazine covalent triazine framework material shows that the prepared phenoxazine covalent triazine framework material has a porous structure and the specific surface area is 1131m2/g。
Example 6
Preparation of phenothiazine covalent triazine framework material:
adding 0.25mmol of 2, 7-dicyano-10-methylphenothiazine and 1.25mmol of zinc chloride into a 10mL ampoule bottle, then sintering and sealing the ampoule bottle under the vacuum condition, heating the reaction mixture to 350 ℃ at the speed of 3 ℃/min in a programmed high-temperature oven, preserving the temperature for 48 hours, and then naturally cooling. 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, tetrahydrofuran, and dichloromethane, respectively, and dried under vacuum at 120 ℃ for 12 hours to obtain black powder with a yield of 55%.
Fourier infrared and X-ray powder diffraction and nitrogen adsorption tests are carried out on the phenothiazine covalent triazine framework material obtained in the embodiment 6 of the invention, the structure, the crystallinity, the specific surface area and the pore size distribution are respectively represented, and the representation results are shown in FIGS. 7-9;
as shown in fig. 7, the infrared spectrum of the obtained phenothiazine covalent triazine framework material shows that characteristic peak of cyano (C ≡ N) in 2, 7-dicyano-10-methylphenothiazine disappears, and triazine (C ≡ N) bond is formed at the same time, thus proving successful preparation of phenothiazine covalent triazine framework material;
as shown in fig. 8, the resulting powder X-ray diffraction pattern of the phenothiazine covalent triazine framework material, the material synthesized by the ionothermal method, appeared amorphous;
as shown in FIG. 9, the obtained nitrogen adsorption and desorption isotherm diagram of the phenothiazine covalent triazine framework material shows that the prepared phenothiazine covalent triazine framework material has a porous structure and the specific surface area is 14m2/g。
Example 7
Preparing a lithium ion battery pole piece containing the phenoxazine or phenothiazine covalent triazine framework material:
respectively weighing 18mg of the phenoxazine or phenothiazine covalent triazine frame materials prepared in the embodiments 5 and 6, ball-milling the materials in a ball mill for 0.5 hour, taking out the materials, adding 9mg of acetylene black, 120mg of PVDF (PVDF with the concentration of 2.5 wt% in N-methyl pyrrolidone) and a certain amount of N-methyl pyrrolidone (NMP), mixing the materials, putting the mixture into the ball mill for ball milling for 2 hours, uniformly mixing, coating the uniformly mixed sample in the ball milling container on a current collector aluminum foil to form a film with the thickness of 200 mu m, drying the film at 80 ℃ for 12 hours, and cutting the dried electrode film into a circular electrode piece with the diameter of 14mm to obtain the lithium ion battery electrode piece of the phenoxazine or phenothiazine covalent triazine frame material.
Example 8
The lithium ion battery assembly comprising the phenoxazine or phenothiazine covalent triazine framework material lithium ion battery pole piece comprises the following components in percentage by weight:
harvesting the fruitThe lithium ion battery electrode plate prepared in example 7 was used as a positive electrode, a metal lithium plate as a negative electrode, a polypropylene microporous membrane (Celgard 2400) as a separator, and 1mol/L LiPF was added6Dissolved in Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (EC/DMC ═ 1: 1v/v) as electrolytes, assembled in a glove box filled with argon, and assembled into a button half cell in a 2016 coin cell case.
And (3) performance characterization:
according to the invention, the button cell containing the phenoxazine or phenothiazine covalent triazine framework material obtained in example 8 is subjected to a cycle stability test, the electrochemical properties of the button cell are characterized, and the characterization results are shown in fig. 10-12.
As shown in fig. 10, the cycle stability test of the prepared phenoxazine and/or phenothiazine covalent organic framework material cell shows that the phenoxazine or phenothiazine covalent triazine framework material has high specific capacity and coulombic efficiency;
as shown in fig. 11, the cyclic voltammetry curve of the prepared phenoxazine or phenothiazine covalent triazine framework material cell shows that the phenoxazine or phenothiazine covalent triazine framework material shows a certain pseudocapacitance controlled lithium storage mechanism;
as shown in fig. 12, the electrochemical impedance spectrum of the prepared phenoxazine and/or phenothiazine covalent organic framework material cell. The results show that the charge transfer resistance of the phenoxazine and/or phenothiazine covalent organic framework materials is 210 Ω and 310 Ω, respectively, indicating rapid redox kinetics.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only 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 disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, 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 its scope. 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 (10)
1. A phenothiazine or phenoxazine dicyano derivative having the structure shown in formula (II):
wherein, X is selected from O or S, and R is selected from any one of linear alkyl, branched alkyl and aromatic ring group.
2. A phenothiazine or phenoxazine dicyano derivative according to claim 1 having the structure shown in formula (III):
wherein R is selected from any one of linear alkyl, branched alkyl and aromatic ring group, preferably any one of methyl, ethyl, isopropyl, phenyl and naphthyl;
alternatively, it has a structure as shown in formula (IV):
wherein R is selected from any one of linear alkyl, branched alkyl and aromatic ring group, preferably any one of methyl, ethyl, isopropyl, phenyl and naphthyl.
3. A process for the preparation of a phenothiazine or phenoxazine dicyano derivative as claimed in claim 1 or claim 2 which comprises:
(1) reacting a first uniformly mixed reaction system containing 4-hydroxy-3-nitrobenzonitrile, a palladium catalyst, a reducing agent and a first solvent at 78 ℃ for 12-16 hours under a protective atmosphere to prepare 4-hydroxy-3-aminobenzonitrile;
(2) reacting a second uniformly mixed reaction system containing the 4-hydroxy-3-aminobenzonitrile, the 3, 4-difluorobenzonitrile, the first alkaline substance and the second solvent at 100 ℃ for 8-12 hours under a protective atmosphere to obtain 2, 7-dicyano-10H-phenoxazine;
(3) and reacting a third mixed reaction system containing the 2, 7-dicyano-10H-phenoxazine, a second basic substance, halogenated hydrocarbon and a third solvent at 25-35 ℃ for 5-10 hours to obtain the 2, 7-dicyano-10-R-phenoxazine.
Or, the preparation method comprises the following steps:
(4) reacting a uniformly mixed reaction system containing 2-chloro-phenothiazine, liquid bromine and acetic acid at room temperature for 24 hours under a protective atmosphere to prepare 2-chloro-7-bromo-10H-phenothiazine;
(5) and reacting the first mixed reaction system containing the 2-chloro-7-bromo-10H-phenothiazine, the first alkaline substance, the halogenated hydrocarbon and the first solvent at room temperature for 1 hour under a protective atmosphere to obtain the 2-chloro-7-bromo-10-R-phenothiazine.
(6) And (3) reacting a second mixed reaction system containing the 2-chloro-7-bromo-10-R-phenothiazine, cuprous cyanide and a second solvent at 140-150 ℃ for 12-24 hours to obtain the 2, 7-dicyano-10-R-phenothiazine.
4. The production method according to claim 3, characterized in that: in the step (1), the molar ratio of the palladium catalyst to the reducing agent of the 4-hydroxy-3-nitrobenzonitrile is 1: 0.1: 20-1: 0.1: 40;
and/or, the reducing agent comprises hydrazine hydrate; the preferred mass concentration of the hydrazine hydrate is 80 wt%;
and/or the first solvent comprises an alcohol solvent and/or a mixed solution of the alcohol solvent and a high-solubility solvent; preferred said alcoholic solvents include methanol and/or ethanol; preferred high solubility solvents include ethyl acetate and/or chloroform;
and/or, the palladium catalyst comprises a palladium on carbon catalyst; preferred palladium on carbon catalysts include: palladium 5 wt%, the remainder comprising activated carbon.
And/or, the preparation method further comprises the following steps: after the reaction of the first uniform mixing reaction system is finished, filtering and purifying the obtained mixture; preferably, the purification treatment comprises extraction and column chromatography separation purification treatment;
and/or the molar ratio of the 4-hydroxy-3-aminobenzonitrile, the 3, 4-difluorobenzonitrile and the first alkaline substance in the step (2) is 1: 1.5-1: 2.5;
and/or, the first alkaline substance comprises potassium hydroxide and/or potassium carbonate;
and/or the second solvent comprises dimethyl sulfoxide and/or N, N-dimethylformamide;
and/or, the preparation method further comprises the following steps: after the reaction of the first uniformly mixed reaction system is finished, filtering, washing and purifying the obtained mixture; preferably the purification treatment comprises: the dried product was washed in ethyl acetate and filtered.
And/or, the protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere;
and/or, the mole ratio of the 2, 7-dicyano-10H-phenoxazine to the second basic substance in the step (3) is 1: 1.5: 2;
and/or the halogenated hydrocarbon comprises R-X, wherein X is selected from any one of F, Cl, Br and I, and R is selected from any one of linear alkyl, branched alkyl and aromatic ring group; preferably, the R is selected from any one of methyl, ethyl, isopropyl, phenyl and naphthyl;
and/or, the second basic substance comprises sodium hydride and/or potassium carbonate;
the third solvent comprises N, N-dimethylformamide and/or dimethyl sulfoxide;
and/or, the protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere;
and/or, the preparation method further comprises the following steps: after the reaction of the first uniformly mixed reaction system is finished, washing, drying and purifying the obtained mixture; preferably the purification treatment comprises: washing and filtering the dried product in ethyl acetate;
and/or, the mole ratio of the 2, 7-dicyano-10H-phenothiazine and the first alkaline substance to the halogenated hydrocarbon in the step (5) is 1: 1.5: 2;
and/or the halogenated hydrocarbon comprises R-X, wherein X is selected from any one of F, Cl, Br and I, and R is selected from any one of linear alkyl, branched alkyl and aromatic ring group; preferably, R is selected from any one of methyl, ethyl, isopropyl, phenyl and naphthyl;
and/or, the first alkaline substance comprises sodium hydride and/or potassium carbonate;
and/or, the first solvent comprises N, N-dimethylformamide and/or dimethyl sulfoxide;
and/or, the protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere;
and/or, the preparation method further comprises the following steps: after the reaction of the first uniformly mixed reaction system is finished, washing, drying and purifying the obtained mixture; preferably the purification treatment comprises: recrystallizing the dried product in toluene;
and/or, the mol ratio of the 2-chloro-7-bromo-10-R-phenothiazine to the cuprous cyanide in the step (6) is 1: 2.4;
and/or the second solvent comprises N, N-dimethylformamide and/or N-methylpyrrolidone;
and/or, the protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere;
and/or, the preparation method further comprises the following steps: after the reaction of the second uniformly mixed reaction system is finished, washing, drying and purifying the obtained mixture; preferably the purification treatment comprises: separating the dried product by column chromatography.
5. Use of a phenoxazine or phenothiazine dicyano derivative according to claim 1 for the preparation of a phenoxazine or phenothiazine covalent triazine framework material.
6. A phenoxazine or phenothiazine covalent triazine framework material, characterized in that it has the structure shown in formula (I):
wherein, X is selected from O or S, and R is selected from any one of linear alkyl, branched alkyl and aromatic ring group.
7. The method of preparing a phenoxazine or phenothiazine covalent triazine framework material of claim 6, comprising: performing ion melting reaction on the phenoxazine or phenothiazine dicyano derivative and zinc chloride, washing the reaction product with water and acid after the reaction is finished, and obtaining the solid which is the phenoxazine or phenothiazine covalent triazine framework material.
And/or the mass ratio of the phenoxazine or phenothiazine dicyano derivative to the zinc chloride is 1: 1-20, and the ion melting reaction conditions are as follows: heating to 350-600 ℃ in a vacuum closed environment, and reacting for 24-72 hours;
and/or the phenoxazine or phenothiazine dicyano derivative is selected from 2, 7-dicyano-10-methylphenoxazine and/or 2, 7-dicyano-10-methylphenthiazine;
preferably, the acid solution is a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 1-5 mol/L;
preferably, the organic solvent is selected from tetrahydrofuran and dichloromethane;
preferably, the drying process comprises: vacuum drying at 50-100 deg.C for 12-24 hr.
8. Use of a phenoxazine or phenothiazine covalent triazine framework material according to claim 6 in a lithium ion battery positive electrode material.
9. A positive electrode for a lithium ion battery, characterized by comprising at least a phenoxazine or phenothiazine covalent triazine framework material as claimed in claim 8.
10. A lithium ion battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that: the positive electrode comprises the lithium ion battery positive electrode of claim 8;
preferably, the preparation method of the lithium ion battery comprises the following steps:
uniformly mixing the phenoxazine or phenothiazine covalent triazine framework material, the conductive agent and the binder according to any one of claims 1 and 6, applying the obtained mixture on a conductive current collector to form a battery anode, and assembling the battery anode, a cathode and an electrolyte into a lithium ion battery; preferably, the conductive current collector comprises an aluminum foil and/or a carbon-coated aluminum foil; preferably, the lithium ion battery comprises a button cell.
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