CN115602839A - High-voltage organic electrode material based on aza-tetracene derivative and preparation method and application thereof - Google Patents

High-voltage organic electrode material based on aza-tetracene derivative and preparation method and application thereof Download PDF

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CN115602839A
CN115602839A CN202211412777.XA CN202211412777A CN115602839A CN 115602839 A CN115602839 A CN 115602839A CN 202211412777 A CN202211412777 A CN 202211412777A CN 115602839 A CN115602839 A CN 115602839A
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electrode material
bpzr
ion battery
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赵宇
叶婧
戴高乐
李明磊
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Hangzhou Normal University
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
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    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • H—ELECTRICITY
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    • 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
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The invention relates to the field of organic electrode materials, and discloses a high-voltage organic electrode material based on aza-tetracene derivatives, and a preparation method and application thereof. The n-conjugated nitrogen heterocyclic aromatic polymer is used as an organic electrode material, and the average molecular weight of each active center is reduced to obtain higher specific capacity. In addition, the electron density of the nitrogen-nitrogen oxide reduction active center can be reduced by the conjugated extension structure of the aza-tetracene derivative, the discharge voltage is further improved, and meanwhile, the stability of a redox intermediate can be improved by charge delocalization on a conjugated skeleton of the conjugated extension multi-electron redox active center unit, so that the cycling stability of the electrode material in the charge-discharge process is improved. Therefore, the lithium sodium ion battery based on the p-BPZR positive electrode has higher voltage, higher specific capacity and energy density and excellent cycling stability.

Description

High-voltage organic electrode material based on aza-tetracene derivative and preparation method and application thereof
Technical Field
The invention relates to the field of secondary batteries, in particular to a high-voltage organic electrode material based on a nitrogen heterocyclic tetracene derivative, and a preparation method and application thereof.
Background
Increasingly serious air pollution, global warming and consumption of fossil fuels are the problems which need to be urgently solved in the sustainable development of society. These challenges can only be addressed by adjusting the existing energy structure to increase the use of environmentally friendly renewable energy. Solar, wind and biomass energy can be converted into electrical energy, but the intermittency and the dispersiveness of these renewable energy sources make them difficult to directly utilize, which requires the development of efficient energy storage systems. Among them, lithium ion batteries have become the main power of portable electronic devices due to their high energy density, long cycle life, and high efficiency, and have attracted extensive commercial and scientific attention in the fields of electric vehicles and smart grids. Currently commercially available lithium ion battery positive electrode materials are mainly based on transition metal oxides and phosphates, but both exhibit significant disadvantages. Therefore, it becomes important to design a new cathode material that is efficient, environmentally friendly and renewable.
Organic electrode materials composed of elements such as C, H, O, N and the like are considered as energy storage materials with wide application prospects due to the metal-free characteristics of large theoretical specific capacity, low production cost, high safety, high natural abundance and easy recovery. More importantly, the diversity of the structure of the organic material makes it possible to adjust its redox properties by structural modification or functionalization. In addition, the organic electrode material based on the conversion reaction is not limited by the number, type, particle size and other factors of the carrier, and can be compatible with various cations or anions, so that the electric energy storage is more diversified. At present, the research on organic electrode materials is mostly focused on n-type materials, and the discharge potential of the materials is generally low, so that the requirements of high energy density and high power density cannot be met. Therefore, more and more research is focused on p-type organic electrode materials having high voltage, however, the trade-off relationship between specific capacity and voltage remains one of the biggest obstacles to the development of organic electrode materials having practical high energy density. Therefore, the development of a metal ion battery having high voltage, high specific capacity, high energy density and good cycle stability is an inevitable problem in realizing large-scale electric energy storage.
Disclosure of Invention
In order to solve the above technical problems, a first object of the present invention is to provide a high voltage organic electrode material based on an azatetracene derivative, which is a p-type organic electrode material having a conjugated polyelectron active center, and which can provide a metal ion battery with a high specific capacity and a high voltage, and also has a high energy density and good cycling stability.
A high-voltage organic electrode material p-BPZR based on aza-tetracene derivatives has a general structural formula:
Figure BDA0003938733630000021
wherein R is 1 、R 2 、R 3 、R 4 Respectively selected from one of H, me, et, iPr, tBu, OMe and OEt;
ar is selected from
Figure BDA0003938733630000022
Figure BDA0003938733630000023
One kind of (1).
Preferably, R 1 、R 2 、R 3 、R 4 Are all H, ar is
Figure BDA0003938733630000024
Figure BDA0003938733630000025
To (3) is provided.
The p-type organic positive electrode material p-BPZR is prepared by copolymerizing a aza-tetracene derivative (5, 12-dihydrobenzo [ b ] phenazine) and different bridging groups. On the one hand, higher specific capacities are obtained by increasing the number of active centers in the monomer and reducing the average molecular weight of each active center. On the other hand, the charge distribution density of the nitrogen-based conjugated organic redox center can be diluted by utilizing the extension of the conjugated skeleton, and the redox potential and the discharge voltage of the battery are further improved.
Experiments prove that the conversion mechanism of the organic anode material is not limited by factors such as the number, the type and the particle size of charge carriers, and when the organic anode material is applied to different types of batteries such as lithium ion batteries and sodium ion batteries, the organic anode material can endow the batteries with higher voltage, specific capacity and power density, and has good cycle stability.
The second purpose of the invention is to provide a preparation method of a high-voltage organic electrode material p-BPZR based on an azatetracene derivative, which comprises the following steps:
step (1) Synthesis of 5, 12-dihydrobenzo [ b ] phenazine
2, 3-dihydroxynaphthalene and o-phenylenediamine were separately ground and mixed, and oxygen was removed 3 times by a freeze-vacuum-thaw cycle. Carrying out solid-phase reaction on the mixture after the deoxidization at 180 ℃ for 30 minutes to obtain a crude product, cooling the crude product to room temperature, grinding the crude product by using a mortar, washing the crude product by using methanol, acetone and ether respectively, and finally carrying out vacuum drying to obtain light yellow 5, 12-dihydrobenzo [ b ] phenazine powder;
step (2) synthesizing an organic anode material p-BPZR
Degassing the 5, 12-dihydrobenzo [ b ] phenazine prepared in the step (1), an aromatic compound and sodium tert-butoxide in anhydrous xylene to obtain a solution I; degassing palladium acetate and 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl in anhydrous xylene to obtain a solution II;
adding the solution II into the solution I, and removing oxygen through three freeze pumps-unfreezing circulation to obtain a mixture solution III; stirring the mixture solution III for 24 hours at 120 ℃ under the conditions of nitrogen atmosphere and reflux condensation, then heating to 140 ℃, stirring for 12 hours, and finally adding iodobenzene for carrying out end-capping reaction for 5 hours to obtain a crude product; after the crude product had cooled to room temperature, it was filtered and dispersed in H sequentially by means of a mortar and ultrasound 2 O、EtOH、DCM、DMF、THF. And (3) washing, filtering and purifying the EC and DEC mixed solution and EA with the volume ratio of 1. After repeating the process for three times, the product is dried in vacuum to obtain the organic anode material p-BPZR.
The aromatic compound is
Figure BDA0003938733630000031
Figure BDA0003938733630000032
Wherein X is halogen.
Preferably, X is bromine.
Preferably, the molar ratio of the 2, 3-dihydroxynaphthalene to the o-phenylenediamine is 1:1.
preferably, the molar ratio of 5, 12-dihydrobenzo [ b ] phenazine to aromatic compound is 1:1.
preferably, the molar ratio of the palladium acetate, 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl and 5, 12-dihydrobenzo [ b ] phenazine is 0.08-0.15: 0.16 to 0.3:1.
a third object of the present invention is to provide a battery positive electrode comprising the above-mentioned high voltage organic electrode material p-BPZR based on an azatetracene derivative, a conductive agent, a binder and a current collecting aluminum foil.
preparing a p-BPZR positive electrode: adding a solvent N, N-dimethyl pyrrolidone (NMP) into an active material p-BPZR, a conductive agent and a binder according to a certain mass ratio (6-9, 0.5-3) and uniformly mixing, coating the mixture on a positive current collector and drying, and cutting the dried mixture into electrode plates with proper sizes, namely p-BPZR positive electrode plates.
The thickness of the slurry layer of the p-BPZR positive pole piece is 50-100 mu m.
The fourth purpose of the invention is to provide a metal-ion battery, which adopts the battery anode.
Preferably, the metal ion battery includes a lithium ion battery or a sodium ion battery, and specifically includes:
the lithium ion battery comprises a p-BPZR positive electrode, a diaphragm, a negative electrode and lithium salt electrolyte; whereinThe negative electrode is generally a lithium plate, and the lithium salt electrolyte is LiTFSI, liPF 6 And lithium salt is dissolved in organic solvent to prepare 0.5-1.5M lithium salt solution.
The sodium ion battery comprises a p-BPZR anode, a diaphragm, a cathode and sodium salt electrolyte; wherein the negative electrode is sodium sheet, and the sodium salt electrolyte is NaClO 4 ，NaPF 6 And dissolving sodium salt in organic solvent to prepare 0.5-1.5M sodium salt solution.
The invention has the following beneficial effects:
(1) The invention adopts a structure of multi-electron redox active centers, in particular to a pi-conjugated nitrogen heterocyclic aromatic polymer, and obtains higher specific capacity by increasing the number of active centers in a monomer and reducing the average molecular weight of each active center.
(2) According to the invention, the aza-tetracene derivative (5, 12-dihydrobenzo [ b ] phenazine) is used as an active center unit, the conjugated ductile structure is utilized to reduce nitrogen oxide to reduce the electron density of the active center, the discharge voltage of the battery is further improved, and meanwhile, the multi-electron redox active center unit can improve the stability of a redox intermediate through charge delocalization on a conjugated framework, so that the cycling stability of the electrode material in the charging and discharging process is improved.
(3) The polymer p-BPZR is used as the organic anode material, so that the dissolution of the organic micromolecule material in the electrolyte can be reduced, and the problems of internal short circuit, rapid reduction of battery capacity and the like are avoided. This is all favorable for the battery to have higher voltage, specific capacity, energy density and good cycling stability.
Drawings
FIG. 1 is a synthesis scheme of an organic cathode material p-BPZ1 in example 1.
FIG. 2 shows the synthesis scheme of p-BPZ2, an organic cathode material in example 2.
FIG. 3 is a synthetic route of the organic positive electrode material p-BPZ3 in example 3.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of 5, 12-dihydrobenzo [ b ] phenazine obtained in example 1.
FIG. 5 is a mass spectrum of 5, 12-dihydrobenzo [ b ] phenazine obtained in example 1.
Fig. 6 is a mass spectrum of the organic cathode material obtained in example 1.
Fig. 7 is a scanning electron micrograph of the organic cathode material obtained in example 1.
Fig. 8 is a powder diffraction XRD pattern of the organic cathode material obtained in example 1.
Fig. 9 is a TGA analysis chart of thermogravimetric analysis of the organic cathode material obtained in example 1.
Fig. 10 is a differential scanning calorimetry DSC analysis of the organic cathode material obtained in example 1.
Fig. 11 is a charge/discharge curve at a 1C rate of a lithium ion battery using p-BPZ1 as a positive electrode material in application example 1.
Fig. 12 is a charge-discharge long cycle diagram at a 1C rate of a lithium ion battery using p-BPZ1 as a positive electrode material in application example 1.
Fig. 13 is a graph showing the rate cycles at 0.5 to 5C for a lithium ion battery using p-BPZ1 as a positive electrode material in application example 1.
Fig. 14 is a charge/discharge curve at a 1C rate of a sodium ion battery using p-BPZ1 as a positive electrode material in application example 2.
Fig. 15 is a charge-discharge long cycle diagram at a rate of 1C of a sodium ion battery using p-BPZ1 as a positive electrode material in application example 2.
Detailed Description
The present invention will be described in detail below by way of examples.
In a first aspect, the invention provides a high-voltage organic electrode material p-BPZR based on an azatetracene derivative, which has a structural general formula as follows:
Figure BDA0003938733630000051
wherein R is 1 、R 2 、R 3 、R 4 Each is independently selected from one of H, me, et, iPr, tBu, OMe and OEt;
ar is selected from
Figure BDA0003938733630000052
Figure BDA0003938733630000053
One of (1);
in a second aspect, the invention provides a method for preparing the high-voltage organic electrode material p-BPZR based on the azatetracene derivative, which comprises the following specific steps:
step (1) Synthesis of 5, 12-dihydrobenzo [ b ] phenazine
Respectively grinding and mixing 37.5mmol 2, 3-dihydroxynaphthalene and 37.5mmol o-phenylenediamine, and removing oxygen for 3 times through a freezing-vacuum-melting cycle; carrying out solid-phase reaction on the deaerated mixture at 180 ℃ for 30 minutes to prepare a crude product, cooling to room temperature, grinding, washing with methanol, acetone and ether respectively, and finally carrying out vacuum drying to obtain a product 5, 12-dihydrobenzo [ b ] phenazine;
step (2) synthesizing an organic electrode material p-BPZR
Degassing 1.5mmol of 5, 12-dihydrobenzo [ b ] phenazine, 1.5mmol of an aromatic compound and 4.5mmol of sodium tert-butoxide in anhydrous xylene (25 mL) to obtain a solution I; degassing 0.15mmol of palladium acetate and 0.3mmol of 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl in anhydrous xylene (10 mL) to obtain a solution II;
adding the solution II into the solution I, and removing oxygen through three freeze pumps-unfreezing circulation to obtain a mixture solution III; stirring the mixture solution III for 24h at 120 ℃ under the conditions of nitrogen atmosphere and reflux condensation, then heating to 140 ℃ and stirring for 12h, finally adding 0.5mL of iodobenzene for end-capping reaction for 5h, and cooling to room temperature to obtain a crude product;
the crude product was filtered and dispersed in sequence in H by mortar and sonication 2 O, etOH, DCM, DMF, THF, EC/DEC (1. After repeating the process for three times, carrying out vacuum drying on the product to obtain an organic electrode material p-BPZR;
the aromatic compound is
Figure BDA0003938733630000061
Figure BDA0003938733630000062
Wherein X is halogen.
In a third aspect, the present invention provides a battery positive electrode comprising the above-mentioned high-voltage organic electrode material p-BPZR based on an azatetracene derivative, a conductive agent, a binder and a current-collecting aluminum foil; wherein the mass ratio of the high-voltage organic electrode material p-BPZR based on the azatetracene derivative, the conductive agent and the binder is 6-9:0.5-3:0.5-3.
In a fourth aspect, the present invention provides a metal-ion battery, including a lithium-ion battery or a sodium-ion battery. The metal ion battery employs P-BPZR as a positive electrode material, the positive electrode material, super P and polyvinylidene fluoride were mixed in N-methyl-2-pyrrolidone (anhydrous) at a weight ratio of 6. The slurry was then cast on an aluminum foil of 50 μm thickness, dried at 65 ℃ under vacuum for 12h at 10 MPa-cm -2 Is pressed under pressure and cut into disks having a diameter of 10 mm. Batteries were stored in a glove box (H) using standard CR2032 coin cell batteries 2 O and O 2 Concentration of<1 ppm) of lithium metal sheet as negative electrode, celgard 2500 as separator, 1M LiPF 6 The EC/DEC (1, v; instead of using a metal sodium sheet as a negative electrode, a glass fiber film as a separator, 1M NaClO 4 in PC(100Vol％with 5.0％FEC 1M LiPF 6 ) As an electrolyte, a sodium ion battery was produced.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be 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.
Example 1: synthesis of p-BPZ1
When R1, R2, R3, R4= H,
Figure BDA0003938733630000071
the structural formula of p-BPZ1 is as follows:
Figure BDA0003938733630000072
the synthetic route of the p-BPZ1 is shown in figure 1, and the specific synthetic steps are as follows:
step (1), synthesis of 5, 12-dihydrobenzo [ b ] phenazine:
2, 3-dihydroxynaphthalene (6 g,37.5 mmol) and o-phenylenediamine (4.05g, 37.5 mmol) were separately ground and charged into a single-neck flask, and oxygen was removed 3 times by a freeze-vacuum-thaw cycle. The mixture was subjected to solid-phase reaction at 180 ℃ for 30 minutes. The crude product was cooled to room temperature, ground in a mortar, washed with methanol, acetone and ether, and finally dried in vacuum to give a pale yellow powder with a yield of 59%.
The obtained 5, 12-dihydrobenzo [ b ] phenazine was characterized by NMR and mass spectra, and the results are shown in FIGS. 4 and 5, respectively.
Step (2), synthesis of p-BPZ 1:
reacting 5, 12-dihydrobenzo [ b ]]Phenazine (350mg, 1.5 mmol), 1, 4-dibromobenzene (354.2mg, 1.5 mmol) and sodium tert-butoxide (432mg, 4.5 mmol) were degassed in anhydrous xylene (25 mL) to give solution A 1 (ii) a While palladium acetate (34mg, 0.15mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (143m g, 0.3mmol) was degassed in anhydrous xylene (10 mL) to obtain a solution A 2 . Mixing the solution A 2 Adding solution A 1 To obtain a mixed solution A 3 After oxygen removal through three freeze pump-thaw cycles, the mixed solution A is 3 In the nitrogen atmosphere and the reflux condensation condition, firstly stirring for 24 hours at 120 ℃, then heating to 140 ℃, stirring for 12 hours, and finally adding 0.5mL iodobenzene for end capping reaction for 5 hours. After cooling to room temperature, the mixture was filtered and the product was dispersed in H by mortar and sonication in succession 2 O, etOH, DCM, DMF, THF, EC/DEC (1. Heavy loadAfter repeating the process for three times, the product is dried in vacuum to obtain the organic cathode material (p-BPZ 1).
Mass spectrum characterization was performed on the obtained p-BPZ1, and the results are shown in FIG. 6, wherein the degree of polymerization is mainly 5 to 7.
The morphology of the polymer p-BPZ1 sample was observed with a Scanning Electron Microscope (SEM), as shown in FIG. 7. The purified polymer p-BPZ1 material showed irregular bulk particles ranging in size from 1 to 5 μm.
Powder X-ray diffraction (XRD) analysis of the crystalline structure of polymer p-PZ revealed two broad diffraction peaks in the small and wide angle regions, respectively, as shown in FIG. 8. The two diffraction peaks in the wide-angle area are weak and wide, which indicates that the material is in an amorphous structure and reflects that the pi-pi stacking distance between oligomer skeletons is effectively inhibited. While a broad diffraction peak in the small angle region indicates the presence of a locally ordered structure between the rigid monomers of the p-PZ chain.
Thermogravimetric analysis (TGA) and Differential Scanning Calorimeter (DSC) measurements are shown in fig. 9 and 10, and the results indicate that p-BPZ1 decomposes at about 347 ℃ under an air atmosphere; whereas in a nitrogen atmosphere, p-BPZ1 decomposes at about 406 ℃. The p-BPZ1 does not melt or change phase in the temperature range of 0-300 ℃, namely the requirement of battery preparation is met.
Example 2: synthesis of p-BPZ2
When R1, R2, R3, R4= H,
Figure BDA0003938733630000081
the structural formula of p-BPZ2 is as follows:
Figure BDA0003938733630000082
the synthetic route of the p-BPZ2 is shown in figure 2, and the specific synthetic steps are as follows:
step (1), synthesis of 5, 12-dihydrobenzo [ b ] phenazine:
2, 3-dihydroxynaphthalene (6 g,37.5 mmol) and o-phenylenediamine (4.05g, 37.5 mmol) were separately ground and charged into a single-neck flask, and oxygen was removed 3 times by a freeze-vacuum-thaw cycle. The mixture was subjected to solid-phase reaction at 180 ℃ for 30 minutes. The crude product was cooled to room temperature, ground in a mortar, washed with methanol, acetone and ether, and finally dried in vacuum to give a pale yellow powder with a yield of 59%.
Step (2), synthesis of p-BPZ 2:
reacting 5, 12-dihydrobenzo [ b ]]Phenazine (350mg, 1.5 mmol), 4' -dibromodiphenyl ether (488.8mg, 1.5 mmol) and sodium tert-butoxide (432mg, 4.5 mmol) were degassed in anhydrous xylene (25 mL) to give solution B 1 (ii) a While palladium acetate (34mg, 0.15mmol) and 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (143m g, 0.3mmol) were degassed in anhydrous xylene (10 mL) to obtain a solution B 2 . Mixing the solution B 2 Adding solution B 1 To obtain a mixed solution B 3 Removing oxygen through three freezing pump-unfreezing cycles, and then mixing the solution B 3 Stirring at 120 ℃ for 24h in a nitrogen atmosphere and under reflux condensation conditions, then heating to 140 ℃ and stirring for 12h, and finally adding 0.5mL of iodobenzene to carry out end capping reaction for 5h. After cooling to room temperature, the mixture was filtered and the product was dispersed in H by mortar and sonication in succession 2 O, etOH, DCM, DMF, THF, EC/DEC (1. After repeating this process three times, the product was vacuum dried to obtain an organic positive electrode material (p-BPZ 2).
Example 3: synthesis of p-BPZ3
When R1, R2, R3, R4= H,
Figure BDA0003938733630000091
the structural formula of p-BPZ3 is as follows:
Figure BDA0003938733630000092
the synthesis route of the p-BPZ3 is shown in figure 3, and the specific synthesis steps are as follows:
step (1), synthesis of 5, 12-dihydrobenzo [ b ] phenazine:
2, 3-dihydroxynaphthalene (6 g,37.5 mmol) and o-phenylenediamine (4.05g, 37.5 mmol) were separately ground and charged into a single-neck flask, and oxygen was removed 3 times by a freeze-vacuum-thaw cycle. The mixture was subjected to solid phase reaction at 180 ℃ for 30 minutes. The crude product was cooled to room temperature, ground in a mortar, washed with methanol, acetone and ether, respectively, and finally dried in vacuo to give a pale yellow powder in 59% yield.
Step (2), synthesis of p-BPZ 3:
reacting 5, 12-dihydrobenzo [ b ]]Phenazine (350mg, 1.5 mmol), bis (4-bromophenyl) methane (485.9mg, 1.5 mmol) and sodium tert-butoxide (432mg, 4.5 mmol) were degassed in anhydrous xylene (25 mL) to give solution C 1 (ii) a While palladium acetate (34mg, 0.15mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (143m g, 0.3mmol) was degassed in anhydrous xylene (10 mL) to obtain a solution C 2 . Mixing the solution C 2 Adding solution C 1 To obtain a mixed solution C 3 Removing oxygen through three freezing pump-unfreezing cycles, and then mixing the solution C 3 Stirring at 120 ℃ for 24h in a nitrogen atmosphere and under reflux condensation conditions, then heating to 140 ℃ and stirring for 12h, and finally adding 0.5mL of iodobenzene to carry out end capping reaction for 5h. After cooling to room temperature, the mixture was filtered and the product was dispersed in H by mortar and ultrasound in that order 2 O, etOH, DCM, DMF, THF, EC/DEC (1. After repeating this process three times, the product was vacuum-dried to obtain an organic positive electrode material (p-BPZ 3).
Application example 1: lithium ion battery
Using P-BPZ1 produced in example 1 as a positive electrode material, the positive electrode material, super P and polyvinylidene fluoride were mixed in N-methyl-2-pyrrolidone (anhydrous) at a weight ratio of 6. The slurry was then cast on an aluminum foil 50 μm thick, dried in vacuum at 65 ℃ for 12h, at 10MPa cm -2 Is pressed under pressure and cut into disks having a diameter of 10 mm. Batteries were stored in a glove box (H) using standard CR2032 coin cell batteries 2 O and O 2 Concentration of<1 ppm) with a metallic lithium plate as negative electrode, celgard 2500 as separator, 1M LiPF 6 The EC/DEC (1, v.
Fig. 11 is a charge/discharge curve at 1C rate of a lithium ion battery in which p-BPZ1 is used as a positive electrode and a lithium plate is used as a negative electrode. For Li + The polymer p-BPZ1 obtains 3.7V of average high battery discharge voltage, and meanwhile, the initial discharge capacity of the p-BPZ1 at 1C is as high as 151mAh/g and is close to the theoretical specific capacity of 176mAh/g, which indicates that all active centers of the p-BPZ1 participate in the electrochemical reaction.
Fig. 12 is a long cycle diagram of charge and discharge at 1C rate of a lithium ion battery using polymer p-BPZ1 as a positive electrode material. p-BPZ1 has good cycling stability, and the relatively low coulombic efficiency over the first few cycles is due to the formation of a solid electrolyte interfacial layer. During the subsequent 800 charge/discharge cycles, the Coulombic Efficiency (CE) of p-BPZ1 approaches 100%, and the capacity retention rate after 800 cycles is as high as 88%.
FIG. 13 is a graph of the rate cycle of a lithium ion battery with the polymer p-BPZ1 as the positive electrode material under different rates. The results show that the p-BPZ 1-based electrode shows high rate performance, high energy density, and the average capacities of the p-BPZ1 electrode at 0.5, 1, 2 and 5C are 145, 143, 134 and 106mAh g respectively -1 . Corresponding energy densities of up to about 540, 529, 495 and 393Wh kg -1 。
Application example 2: sodium ion battery
The organic cathode materials P-BPZ1, super P and polyvinylidene fluoride prepared in example 1 were mixed in N-methyl-2-pyrrolidone (anhydrous) in a weight ratio of 6. The slurry was then cast on an aluminum foil of 50 μm thickness, dried at 65 ℃ under vacuum for 12h at 10 MPa-cm -2 Is pressed under pressure and cut into disks having a diameter of 10 mm. Batteries were stored in a glove box (H) using standard CR2032 coin cell batteries 2 O and O 2 Concentration of<1 ppm) of a metal sodium sheet as a negative electrode, a glass fiber film as a separator, 1M NaClO 4 in PC(100Vol％with 5.0％FEC 1M LiPF 6 ) As an electrolyte, a sodium ion battery was produced.
Fig. 14 is a charge-discharge curve at 1C rate of a sodium ion battery using the polymer p-BPZ1 shown in example 1 of the present invention as a positive electrode material. The p-BPZ 1-based electrode showed 161mAh g at a rate of 1C in the first cycle -1 The specific capacity of the lithium ion battery is equivalent to that of the lithium ion battery.
Fig. 15 is a charge-discharge long cycle diagram at 1C rate of a sodium ion battery using the polymer p-BPZ1 shown in example 1 of the present invention as a positive electrode material. Since sodium has a larger ion radius than lithium, sodium ion batteries have a faster capacity fade than lithium ion batteries. The polymer p-BPZ1 still has a specific capacity retention rate of 70% after 150 cycles.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (9)

1. A high-voltage organic electrode material p-BPZR based on an azatetracene derivative is characterized by having a structural general formula as follows:
Figure FDA0003938733620000011
wherein R is 1 、R 2 、R 3 、R 4 Each is independently selected from one of H, me, et, iPr, tBu, OMe and OEt;
ar is selected from
Figure FDA0003938733620000012
Figure FDA0003938733620000013
One of (1);
n is a natural number of 5 to 8.
2. A process for the preparation of the high voltage organic electrode material p-BPZR according to claim 1 based on azatetracene derivatives, characterized in that it comprises the following steps:
step (1) Synthesis of 5, 12-dihydrobenzo [ b ] phenazine
Respectively grinding and mixing 2, 3-dihydroxynaphthalene and o-phenylenediamine, and removing oxygen for 3 times through freezing-vacuum-melting circulation; carrying out solid phase reaction on the mixture after the deoxidization at the temperature of 175-180 ℃ for 30-40 minutes to obtain a crude product, cooling the crude product to room temperature, grinding the crude product, washing the crude product with methanol, acetone and ether respectively, and finally carrying out vacuum drying to obtain a product 5, 12-dihydrobenzo [ b ] phenazine;
step (2) synthesizing an organic electrode material p-BPZR
Degassing the 5, 12-dihydrobenzo [ b ] phenazine prepared in the step (1), an aromatic compound and sodium tert-butoxide in anhydrous xylene to obtain a solution I; degassing palladium acetate and 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl in anhydrous xylene to obtain a solution II;
adding the solution II into the solution I, and removing oxygen through three freeze pumps-unfreezing circulation to obtain a mixture solution III; stirring the mixture solution III for 20-24 h at 120-125 ℃ in a nitrogen atmosphere under reflux condensation conditions, then heating to 135-140 ℃ and stirring for 10-12 h, finally adding iodobenzene for end-capping reaction for 5-7 h, and cooling to room temperature to obtain a crude product;
the crude product was filtered and dispersed in sequence in H by mortar and sonication 2 Washing, filtering and purifying in a mixed solution of O, etOH, DCM, DMF, THF, EC and DEC with the volume ratio of 1; repeating the steps for multiple times, and then carrying out vacuum drying on the product to obtain an organic electrode material p-BPZR;
the aromatic compound is
Figure FDA0003938733620000021
Figure FDA0003938733620000022
Wherein X is halogen.
3. The method according to claim 2, wherein the molar ratio of 2, 3-dihydroxynaphthalene to o-phenylenediamine in step (1) is 1:1 to 1.5.
4. The method of claim 2, wherein the molar ratio of 5, 12-dihydrobenzo [ b ] phenazine to aromatic compound in step (2) is 1:1.5.
5. the process according to claim 2, wherein the molar ratio of palladium acetate, 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl and 5, 12-dihydrobenzo [ b ] phenazine in step (2) is 0.08 to 0.15:0.16 to 0.3:1.
6. a positive electrode for a battery comprising the high voltage organic electrode material p-BPZR based on an azatetracene derivative according to claim 1, a conductive agent, a binder and a current collecting aluminum foil.
7. The positive electrode for a battery according to claim 6, wherein the mass ratio of the high-voltage organic electrode material p-BPZR based on the azatetracene derivative, the conductive agent and the binder is 6 to 9:0.5-3:0.5-3.
8. A metal-ion battery, characterized in that the positive electrode of the battery according to claim 6 or 7 is used.
9. The metal-ion battery of claim 8, wherein the metal-ion battery comprises a lithium-ion battery or a sodium-ion battery.
CN202211412777.XA 2022-11-11 2022-11-11 High-voltage organic electrode material based on aza-tetracene derivative and preparation method and application thereof Pending CN115602839A (en)

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