CN115160323B - Conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m and synthetic method and application thereof - Google Patents
Conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m and synthetic method and application thereof Download PDFInfo
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Abstract
The invention discloses a conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m, and a synthesis method and application thereof. The macrocyclic conjugated structure constructed based on the carbazole derivative has outstanding conductivity and high thermal stability, is a good organic pi conjugated conductive material, has the advantage of high conductivity as an organic positive electrode material, and can improve the charge and discharge efficiency of a battery. The construction of the higher molecular weight macrocycle can effectively inhibit the dissolution of the active material in the electrolyte. In addition, the R- (BCz-Ph) m material forms a larger gap through bulk accumulation, is favorable for ion transmission, can adapt to cations with larger ion radius, and is suitable for lithium ion batteries, sodium ion batteries and potassium ion batteries.
Description
Technical Field
The invention relates to the technical field of organic electrode materials, in particular to a conjugated macrocyclic biscarbazole derivative R- (BCz-Ph) m, and a synthesis method and application thereof.
Background
Social evolution has witnessed a rapid evolution of battery technology, starting with lead-acid batteries, to nickel-cadmium, nickel-hydrogen batteries and continuing to Lithium Ion Batteries (LIBs). Since the first commercialization of lithium ion batteries by Sony corporation in 1991, lithium ion batteries have led to the portable electronic market and have shown tremendous promise in large-scale applications such as Electric Vehicles (EV) and smart grids. The great influence of lithium ion batteries on society has also made three researchers stand out in the 2019 nobel chemical prize. The vast application market presents significant challenges to the sustainability and cost problems of electrode materials (especially positive electrode materials). Conventional commercial positive electrode materials mostly use inorganic positive electrodes based on inorganic transition metal oxides and phosphates, such as LiCoO2, liMn2O4, liFePO4, liNixMnyCozO2, and the like. The transition metal resources such as Co, ni and the like are not renewable, the battery recycling technology is complex, the cost is high, and the problems of resource shortage and the like can be possibly faced in the long term. Therefore, low cost green mass production and application batteries require readily available materials.
Organic electrode materials have been attracting attention in recent years because they contain abundant elements such as carbon, hydrogen, and oxygen, and thus exhibit the advantages of being renewable, green, environment-friendly, low-cost, and high-capacity. Firstly, organic electrode materials can be generally extracted directly from plants or prepared by a simple method by taking biomass materials as raw materials. For example, natural sugar inositol can be used to prepare electrochemically active dilithium rhodizonate, which is present in plants such as corn as phytic acid, and likewise, polyquinones are useful redox active molecules, which can be prepared by polycondensation of malic acid; secondly, carbon dioxide generated in the processes of organic material extraction and preparation, battery assembly and recovery can be absorbed and utilized by plants, so that good circulation and reproducibility are reflected. However, organic electrode materials also suffer from problems such as high solubility in the electrolyte, poor conductivity, and low energy density.
Carbazole and its derivative are important nitrogen-containing aromatic heterocyclic compounds, the molecule contains larger conjugated system and strong intramolecular electron transfer, and the special rigid condensed ring structure makes carbazole compound show a plurality of unique performances and biological activities, and has potential wide application in photoelectric materials, dyes, medicines, supermolecule recognition and other fields. The synthesis of carbazole derivatives and the development of potential new uses of carbazole compounds are active research fields in recent years and rapid in development by constructing conjugated macrocycles by utilizing different angles of dinitrogen in different configurations of carbazole motifs in bicarbazole.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects in the prior art and provides a conjugated macrocyclic biscarbazole derivative R- (BCz-Ph) m constructed based on a carbazole derivative, and a synthesis method and application thereof.
The technical scheme adopted for solving the technical problems is as follows: the molecular structural formula of the conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) m is as follows:
wherein n=1, 2,3. m represents the total number of monomers present in the polymeric conjugated macrocycle R- (BCz-Ph) m, m=4, 5,6.
The larger m in the conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m is, the larger the conjugated ring is, the less easily the molecule is dissolved in an organic solvent, and the inhibition of the internal shuttle effect is facilitated, so that the cycling stability of the battery is improved.
In order to optimize the overall performance of the battery, it is necessary to design and coordinate the solubility and specific capacity of the electrode material in its entirety, and therefore, when m=4, the conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) 4 The performance is optimal.
Further, the conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) m is a conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) 4 M=4; the conjugated macrocyclic bicarbazole derivative R- (BCz)-Ph) 4 The molecular structural formula is as follows:
conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) 4 The structure of (2) is relatively stable and is not easy to dissolve in organic solvents; the theoretical specific capacity is higher and is 132mAh g -1 。
The synthetic method of the conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m is characterized by comprising the following steps: the method specifically comprises the following steps:
s1, synthesizing an intermediate monomer BCz-Ph-Br, adding p-bromoiodobenzene, 3 '-dicarbazole, cesium carbonate, palladium acetate, 2-dicyclohexylphosphorus-2', 4',6' -triisopropyl biphenyl and toluene into a 100mL double-neck reaction bottle, removing oxygen 3 times through freezing-vacuum-melting circulation, and carrying out reflux condensation stirring reaction on the mixture at 80 ℃ for 12 hours; the obtained crude product is cooled to room temperature, and is subjected to column chromatography purification (PE: EA=6:1) by silica gel, rf=0.6, and is recrystallized to obtain a white powdery product, namely an intermediate monomer BCz-Ph-Br, wherein a mixed solution of dichloromethane and methanol is needed in the recrystallization process;
s2, performing polymerization reaction to form a cyclic organic molecule, adding the intermediate monomer BCz-Ph-Br,3 '-dicarbazole, cesium carbonate, palladium acetate, 2-dicyclohexyl phosphorus-2', 4',6' -triisopropyl biphenyl and toluene prepared in the S1 into a 100mL double-neck reaction bottle, removing oxygen for 3 times through freezing-vacuum-melting circulation, and performing reflux condensation stirring reaction on the mixture at 100 ℃ for 12 hours; and (3) cooling the obtained crude product to room temperature, washing, filtering and purifying by using a mixture of dichloromethane, triethylamine, ethylene carbonate and diethyl carbonate, ethyl Acetate (EA), methanol and water, and further purifying by using a sublimator to remove small molecules to obtain a light brown product, namely the target product R- (BCz-Ph) m.
Further, the volume ratio of the ethylene carbonate to the diethyl carbonate in the mixture of the ethylene carbonate and the diethyl carbonate in the step S2 is 1:1.
The application of the conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) m is disclosed, and the conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) m is used as an anode active material in an alkali metal ion battery.
Further, the alkali metal ion battery comprises a positive electrode, a negative electrode, a current collector, a diaphragm and electrolyte;
the positive electrode is prepared by taking a positive electrode active material R- (BCz-Ph) m, a conductive agent and a binder as raw materials, and the preparation method comprises the following steps: adding an anode active material R- (BCz-Ph) m, a conductive agent and a binder into an N, N-dimethyl pyrrolidone solvent (NMP), and uniformly mixing to obtain mixed slurry; coating the mixed slurry on a positive electrode current collector and drying (the coating thickness of the mixed slurry is 30-100 mu m), and cutting the dried mixed slurry into electrode plates with the required size to obtain positive electrode plates;
the negative electrode includes, but is not limited to, a lithium metal negative electrode, a sodium metal negative electrode, or a potassium metal negative electrode;
the electrolyte comprises an organic solvent and electrolyte salt; the organic solvent is one or more of Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), propylene Carbonate (PC), ethylene glycol dimethyl ether (DME), fluoroethylene carbonate (FEC), hydrofluoroether (HFE) and fluoroethyl methyl carbonate (FEMC); the electrolyte salt is selected according to the negative electrode of the battery, the electrolyte salt of the lithium metal ion battery is lithium salt, the electrolyte salt of the sodium metal ion battery is sodium salt, and the electrolyte salt of the potassium metal ion battery is potassium salt;
the membrane is a Celgard2500 membrane or a fiberglass membrane.
Further, the mass ratio of the positive electrode active material R- (BCz-Ph) m, the conductive agent and the binder is (6-9): (0.5-3): (0.5-3).
Further, the electrolyte salt of the lithium metal ion battery is lithium hexafluorophosphate or lithium bistrifluoromethylsulfonimide, and the electrolyte salt of the sodium metal ion battery is sodium perchlorate or sodium hexafluorophosphate.
The beneficial effects of the invention are as follows: the invention has the advantages of reasonable design, simple and convenient operation and the following advantages:
(1) Carbazole is a typical electron-rich structure, a macrocyclic conjugated structure is arranged in a molecular structure, the carbazole-derivative-based macrocyclic organic molecule has outstanding conductivity and high thermal stability, has higher carrier migration efficiency, is a good organic pi conjugated conductive material, has the advantage of high conductivity as an organic positive electrode material, and can improve the charge and discharge efficiency of a battery;
(2) The conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) m is relatively stable and is not easy to dissolve in organic solvents. Therefore, when the conjugated macrocyclic biscarbazole derivative R- (BCz-Ph) m is used as an organic electrode material, the dissolution of the electrode material in organic electrolyte is effectively avoided, so that the cycle stability of a battery can be improved;
(3) The carbazole group has a large rigid plane structure, and is used as a monomer to construct a large ring, so that a remarkable gap can be formed, the diffusion and transmission of ions are facilitated, and the electrochemical process of the organic electrode active material is based on a simple redox reaction rather than an intercalation mechanism, so that the conjugated large-ring dicarbazole derivative R- (BCz-Ph) m can adapt to cations with larger ionic radius, and the R- (BCz-Ph) m can be used as an organic positive electrode material in a lithium ion battery and a sodium ion battery and a potassium ion battery with larger ionic radius.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is the formula of R- (BCz-Ph) in example 1 4 Is a synthetic roadmap of (2);
FIG. 2 is the formula of R- (BCz-Ph) in example 1 4 Mass spectrum of (3);
FIG. 3 is the formula of R- (BCz-Ph) in example 1 4 SEM photographs of (2);
FIG. 4 is the formula of R- (BCz-Ph) in example 1 4 XRD powder diffraction pattern of (2);
FIG. 5 is a graph of the R- (BCz-Ph) -based composition of example 1 4 A charge-discharge curve diagram of the lithium ion battery of the positive electrode under the 2C multiplying power;
FIG. 6 is a graph of the R- (BCz-Ph) -based composition of example 1 4 An electrochemical long cycle chart of the lithium ion battery of the positive electrode under the 2C multiplying power;
FIG. 7 is an implementationIn example 1, R- (BCz-Ph) is based 4 A charge-discharge curve diagram of the lithium ion battery of the positive electrode under the 5C multiplying power;
FIG. 8 is a graph of the R- (BCz-Ph) -based composition of example 1 4 An electrochemical long cycle chart of the lithium ion battery of the positive electrode under the 5C multiplying power; based on
FIG. 9 is the formula of R- (BCz-Ph) in example 1 4 Electrochemical cycle diagrams of the positive lithium ion battery at 1,3,5, 10 and 20C multiplying power respectively;
FIG. 10 is a graph based on R- (BCz-Ph) in example 1 4 GITT test chart of positive lithium ion battery.
Detailed Description
The invention will now be described in further detail with reference to the drawings and a preferred embodiment. The drawings are simplified schematic representations which merely illustrate the basic structure of the invention and therefore show only the structures which are relevant to the invention.
Example 1
Conjugated macrocyclic biscarbazole derivative R- (BCz-Ph) 4 The molecular structural formula is as follows:
such conjugated macrocyclic bicarbazole derivatives R- (BCz-Ph) 4 As shown in fig. 1, the synthesis method specifically comprises the following steps:
s1, synthesizing an intermediate monomer BCz-Ph-Br, adding p-bromoiodobenzene (8.49 g,30 mmol), 3 '-dicarbazole (3.32 g,10 mmol), cesium carbonate (9.77 g,30 mmol), palladium acetate (135 mg,0.6 mmol), 2-dicyclohexylphosphorus-2', 4',6' -triisopropylbiphenyl (578mg, 1.2 mmol) and 30mL of toluene into a 100mL double-necked reaction bottle, removing oxygen 3 times through freeze-vacuum-thaw cycle, and reflux-condensing and stirring the mixture at 80 ℃ for reaction for 12 hours; after cooling the crude product to room temperature, column chromatography purification with silica gel (PE: ea=6:1), rf=0.6, and recrystallization (dichloromethane and methanol mixture) gave 3.85g of intermediate as a white powder with a yield of about 60%;
s2, forming a cyclic organic molecule by polymerizationThe intermediate monomer BCz-Ph-Br (2.57 g,4 mmol) prepared in S1, 3 '-bicarbazole (1.33 g,4 mmol), cesium carbonate (3.91 g,12 mmol), palladium acetate (90 mg,0.4 mmol), 2-dicyclohexylphosphorus-2', 4',6' -triisopropylbiphenyl (3831 mg,0.8 mmol) and 20mL of toluene were added to a 100mL double-necked flask, oxygen was removed 3 times by freeze-vacuum-thaw cycle, and the mixture was refluxed, condensed and stirred at 100℃for reaction for 12 hours; after the obtained crude product is cooled to room temperature, the crude product is washed, filtered and purified by using methylene dichloride (50 mL), triethylamine (50 mL), a mixture (50 mL) of ethylene carbonate and diethyl carbonate, ethyl Acetate (EA) (50 mL), methanol (50 mL) and water (50 mL), and then the light brown product is obtained by further purifying and removing small molecules by a sublimator to obtain 2.60g of a light brown product, namely the conjugated macrocyclic organic molecule R- (BCz-Ph) of the target product 4 。
The volume ratio of the ethylene carbonate to the diethyl carbonate in the mixture of the ethylene carbonate and the diethyl carbonate in the step S2 is 1:1.
FIG. 2 is R- (BCz-Ph) 4 Is a mass spectrum of (3).
FIG. 3 is R- (BCz-Ph) 4 SEM photographs of (c), the figure shows: r- (BCz-Ph) 4 The macrocyclic molecules have an irregular crumb-like morphology with irregular void pores.
FIG. 4 is R- (BCz-Ph) 4 The XRD powder diffraction pattern of (2) shows: the carbazole group has a rigid planar structure, and R- (BCz-Ph) 4 Has a crystal diffraction peak in the range of 10-25 DEG in the XRD powder diffraction pattern of (2), R- (BCz-Ph) 4 Has an irregular crystal structure.
The conjugated macrocyclic biscarbazole derivative R- (BCz-Ph) 4 The application of the cathode active material in the lithium ion battery is as follows:
based on R- (BCz-Ph) 4 Preparing an organic positive electrode plate: conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) 4 The conductive agent and the binder are prepared according to the mass ratio of 7:2:1, adding solvent N, N-dimethyl pyrrolidone (NMP) and mixing uniformly, coating on a positive current collector, drying, and cutting into electrode slices with proper size after the drying is finished, namely R- (BCz-Ph) 4 And a positive pole piece. R- (BCz-Ph) 4 The thickness of the positive pole piece is50μm。
To prepare R- (BCz-Ph) 4 The positive electrode plate is used as a positive electrode, the metal lithium plate is used as a negative electrode, the FEC/HFE/FEMC solution of 1.0M LiPF and 0.02M LiDFOB is used as electrolyte, and the Celgard2500 film is used as a diaphragm to assemble the button cell. The mass ratio of FEC, HFE and FEMC in the FEC/HFE/FEMC solution was 2:2:6.
FIG. 5 is based on R- (BCz-Ph) 4 Charge-discharge curve diagram of a positive lithium ion battery at 2C rate, which shows that: the charge-discharge platform is relatively high, about 3.8-4.3V, and the first-turn discharge capacity is 124.2mAh g -1 。
FIG. 6 is based on R- (BCz-Ph) 4 Electrochemical long cycle diagram of a positive lithium ion battery at 2C magnification, which shows: the battery is stable in circulation, the coulomb efficiency is up to 98.9%, and the capacity retention rate of 500 circles is up to 80%.
FIG. 7 is based on R- (BCz-Ph) 4 Charge-discharge curve diagram of a positive lithium ion battery at 5C rate, which shows that: the battery has excellent rate performance, shows a gentle charge and discharge platform under the high-rate charge and discharge condition of 5C, has higher charge and discharge voltage (3.8-4.3V) and higher initial-ring discharge capacity of 130.7mAh g -1 。
FIG. 8 is based on R- (BCz-Ph) 4 Electrochemical long cycle diagram of a positive lithium ion battery at 5C magnification, which shows: the battery has high coulombic efficiency (99.9%) at high rate, high cycling stability (81% capacity retention after 500 cycles), and higher energy efficiency (94.1%).
FIG. 9 is based on R- (BCz-Ph) 4 Electrochemical cycle diagrams of positive lithium ion batteries at 1,3,5, 10, 20C rates, respectively, show that: according to the charge and discharge tests of different multiplying powers, the positive electrode material R- (BCz-Ph) based on the invention is fully proved 4 The lithium ion battery has excellent rate performance. The cell exhibited 314, 187Wh kg at high rates of 10C and 20C, respectively -1 Is a high energy density of 3142, 3736, wkg) -1 Is a high power density of (a).
FIG. 10 is based on R- (BCz-Ph) 4 GITT test chart of positive lithium ion battery, which shows: r- (-BCz-Ph) 4 The positive electrode shows high lithium ion diffusion rate, and 8x 10 during charging -13 ～10 -13 cm -2 s -1 3x 10 when discharged -14 ～10 - 13 cm -2 s -1 。
Example 2
The difference from example 1 is that:
conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) 4 The application of the cathode active material in the lithium ion battery is as follows:
based on R- (BCz-Ph) 4 Preparing an organic positive electrode plate: conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) 4 The mass ratio of the conductive agent to the binder is 6:3:1, adding solvent N, N-dimethyl pyrrolidone (NMP) and mixing uniformly, coating on a positive current collector, drying, and cutting into electrode slices with proper size after the drying is finished, namely R- (BCz-Ph) 4 And a positive pole piece. R- (BCz-Ph) 4 The thickness of the positive electrode sheet is 75 μm.
To prepare R- (BCz-Ph) 4 The positive electrode plate is used as a positive electrode, the metal lithium plate is used as a negative electrode, the FEC/HFE/FEMC solution of 1.0M LiPF and 0.02M LiDFOB is used as electrolyte, and the Celgard2500 film is used as a diaphragm to assemble the button cell. The mass ratio of FEC, HFE and FEMC in the FEC/HFE/FEMC solution was 2:2:6.
Example 3
The difference from example 1 is that:
conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) 4 The application of the cathode active material in sodium ion batteries is as follows:
based on R- (BCz-Ph) 4 Preparing an organic positive electrode plate: conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) 4 The conductive agent and the binder are prepared according to the mass ratio of 7:2:1, adding solvent N, N-dimethyl pyrrolidone (NMP) and mixing uniformly, coating on a positive current collector, drying, and cutting into electrode slices with proper size after the drying is finished, namely R- (BCz-Ph) 4 And a positive pole piece. R- (BCz-Ph) 4 The thickness of the positive electrode sheet is 50 μm.
To prepare the R- (BCz)-Ph) 4 The positive electrode plate is used as a positive electrode, the metal sodium plate is used as a negative electrode, and 1.0MNaClO is used as a negative electrode 4 The FEC/HFE/FEMC solution is used as electrolyte, the glass fiber film is used as a diaphragm, and the button cell is assembled. The mass ratio of FEC, HFE and FEMC in the FEC/HFE/FEMC solution was 2:2:6.
Example 4
The difference from example 1 is that:
conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) 4 The application of the cathode active material in sodium ion batteries is as follows:
based on R- (BCz-Ph) 4 Preparing an organic positive electrode plate: conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) 4 The mass ratio of the conductive agent to the binder is 6:3:1, adding solvent N, N-dimethyl pyrrolidone (NMP) and mixing uniformly, coating on a positive current collector, drying, and cutting into electrode slices with proper size after the drying is finished, namely R- (BCz-Ph) 4 And a positive pole piece. R- (BCz-Ph) 4 The thickness of the positive electrode sheet is 75 μm.
To prepare R- (BCz-Ph) 4 The positive electrode plate is used as a positive electrode, the metal sodium plate is used as a negative electrode, and 1.0MNaClO is used as a negative electrode 4 The FEC/HFE/FEMC solution is used as electrolyte, the glass fiber film is used as a diaphragm, and the button cell is assembled. The mass ratio of FEC, HFE and FEMC in the FEC/HFE/FEMC solution was 2:2:6.
The foregoing description is merely illustrative of specific embodiments of the invention, and the invention is not limited to the details shown, since modifications and variations of the foregoing embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (7)
1. A conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m, characterized in that: the conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) m is a conjugated macrocyclic bicarbazole derivative R- (BCz-Ph) 4 M=4; the conjugated macrocyclic biscarbazole derivative R- (BCz-Ph) 4 The molecular structural formula is as follows:
。
2. a method for synthesizing a conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m as defined in claim 1, characterized in that: the method specifically comprises the following steps:
s1, synthesizing an intermediate monomer BCz-Ph-Br, adding p-bromoiodobenzene, 3 '-dicarbazole, cesium carbonate, palladium acetate, 2-dicyclohexylphosphorus-2', 4',6' -triisopropyl biphenyl and toluene into a 100mL double-neck reaction bottle, removing oxygen 3 times through freezing-vacuum-melting circulation, and carrying out reflux condensation stirring reaction on the mixture at 80 ℃ for 12 hours; cooling the obtained crude product to room temperature, performing column chromatography purification on PE (polyethylene) with EA=6:1 and Rf=0.6 by using silica gel, and recrystallizing to obtain a white powdery product, namely an intermediate monomer BCz-Ph-Br, wherein a mixed solution of dichloromethane and methanol is required in the recrystallization process;
s2, performing polymerization reaction to form a cyclic organic molecule, adding the intermediate monomer BCz-Ph-Br,3 '-dicarbazole, cesium carbonate, palladium acetate, 2-dicyclohexyl phosphorus-2', 4',6' -triisopropyl biphenyl and toluene prepared in the S1 into a 100mL double-neck reaction bottle, removing oxygen for 3 times through freezing-vacuum-melting circulation, and performing reflux condensation stirring reaction on the mixture at 100 ℃ for 12 hours; after the obtained crude product is cooled to room temperature, the mixture of dichloromethane, triethylamine, ethylene carbonate and diethyl carbonate, ethyl acetate, methanol and water are used for washing, filtering and purifying, and small molecules are further purified and removed by a sublimator to obtain a light brown product, namely the target product R- (BCz-Ph) 4 。
3. The method for synthesizing the conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m according to claim 2, wherein the method is characterized in that: the volume ratio of the ethylene carbonate to the diethyl carbonate in the mixture of the ethylene carbonate and the diethyl carbonate in the step S2 is 1:1.
4. Use of a conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m as defined in claim 1, characterized in that: the conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m is used as an anode active material and applied to an alkali metal ion battery.
5. The use of a conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m as defined in claim 4, characterized in that: the alkali metal ion battery comprises a positive electrode, a negative electrode, a current collector, a diaphragm and electrolyte;
the positive electrode is prepared by taking a positive electrode active material R- (BCz-Ph) m, a conductive agent and a binder as raw materials, and the preparation method comprises the following steps: adding an anode active material R- (BCz-Ph) m, a conductive agent and a binder into an N, N-dimethyl pyrrolidone solvent, and uniformly mixing to obtain mixed slurry; coating the mixed slurry on a positive electrode current collector, drying, and cutting into electrode plates with required sizes after the drying is finished, namely a positive electrode plate;
the negative electrode comprises a lithium metal negative electrode, a sodium metal negative electrode or a potassium metal negative electrode;
the electrolyte comprises an organic solvent and electrolyte salt; the organic solvent is one or more of ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, ethylene glycol dimethyl ether, fluoroethylene carbonate, hydrofluoroether and fluoroethyl methyl carbonate; the electrolyte salt is selected according to the negative electrode of the battery, the electrolyte salt of the lithium metal ion battery is lithium salt, the electrolyte salt of the sodium metal ion battery is sodium salt, and the electrolyte salt of the potassium metal ion battery is potassium salt;
the membrane is a Celgard2500 membrane or a fiberglass membrane.
6. The use of a conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m as defined in claim 4, characterized in that: the mass ratio of the positive electrode active material R- (BCz-Ph) m to the conductive agent to the binder is (6-9): (0.5-3): (0.5-3).
7. The use of a conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m as defined in claim 4, characterized in that: the electrolyte salt of the lithium metal ion battery is lithium hexafluorophosphate or lithium bistrifluoromethylsulfonyl imide, and the electrolyte salt of the sodium metal ion battery is sodium perchlorate or sodium hexafluorophosphate.
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| JP2007110097A (en) * | 2005-09-14 | 2007-04-26 | Konica Minolta Holdings Inc | Organic electroluminescence element, method of manufacturing same, display, and lighting fixture |
| WO2013111713A1 (en) * | 2012-01-23 | 2013-08-01 | 日産化学工業株式会社 | Carbazole polymer |
| JP2014098061A (en) * | 2012-11-13 | 2014-05-29 | Kyoto Univ | Polymer having carbazole group, monomer having carbazole group, and compound |
| CN111261872A (en) * | 2020-01-21 | 2020-06-09 | 天津大学 | Organic electrode material and preparation method and application thereof |
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| JP2007110097A (en) * | 2005-09-14 | 2007-04-26 | Konica Minolta Holdings Inc | Organic electroluminescence element, method of manufacturing same, display, and lighting fixture |
| WO2013111713A1 (en) * | 2012-01-23 | 2013-08-01 | 日産化学工業株式会社 | Carbazole polymer |
| CN104066766A (en) * | 2012-01-23 | 2014-09-24 | 日产化学工业株式会社 | Carbazole polymer |
| JP2014098061A (en) * | 2012-11-13 | 2014-05-29 | Kyoto Univ | Polymer having carbazole group, monomer having carbazole group, and compound |
| CN111261872A (en) * | 2020-01-21 | 2020-06-09 | 天津大学 | Organic electrode material and preparation method and application thereof |
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