CN113979957B - Self-crosslinking cross-shaped organic positive electrode material and preparation method and application thereof - Google Patents

Self-crosslinking cross-shaped organic positive electrode material and preparation method and application thereof Download PDF

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CN113979957B
CN113979957B CN202111055404.7A CN202111055404A CN113979957B CN 113979957 B CN113979957 B CN 113979957B CN 202111055404 A CN202111055404 A CN 202111055404A CN 113979957 B CN113979957 B CN 113979957B
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bromo
fluoro
dihydrophenazine
phenylaniline
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CN113979957A (en
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赵宇
戴高乐
李华梅
叶婧
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Hangzhou Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/46—Phenazines
    • 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
    • H01M4/36—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
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the field of organic electrode materials, and discloses a self-crosslinking cross-shaped organic anode material as well as a preparation method and application thereof. The self-crosslinking cross-shaped organic anode material directly couples and connects p-type rigid active center dihydrophenazine and another p-type rigid active center diphenylphenazine unit. In the organic anode material, a torsion angle close to 90 degrees is formed between two adjacent active monomers, so that the breaking of (accumulation and formation of a gap which is beneficial to ion diffusion and is similar to an ion transmission channel) between polymer chains is facilitated, a battery can meet high specific capacity and realize high voltage, and the battery is endowed with high energy density, power density and rate capability.

Description

Self-crosslinking cross-shaped organic positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the field of organic electrode materials, in particular to a self-crosslinking cross-shaped organic anode material and a preparation method and application thereof.
Background
As society develops toward sustainable energy production and utilization, the demand for batteries with higher energy density, more environmental protection, and more economy is increasing. However, the lithium ion battery which occupies the market dominance depends on the anode based on the transition heavy metal, the heavy metal resource is limited, and the cost is high. In addition, the available capacity of conventional transition metal oxide-based anodes has reached a theoretical limit, impeding further development of high energy density rechargeable batteries. In this respect, redox active organic materials (ROMs) have high theoretical capacity, structural diversity, design flexibility, potential sustainable production, low cost and low carbon, are mainly composed of abundant elements such as C, H, O, N, etc., and as potential substitutes for traditional inorganic materials, organic electrode materials are promising candidates for next-generation energy storage systems.
The construction of multi-electron active center ROMs is receiving more and more attention, and through the strategy, the average molecular weight of each transferred electron of the electrode material is reduced, so that the overall theoretical capacity is improved. Organic small molecule materials are generally readily soluble in common organic electrolytes, resulting in internal short circuits and rapid degradation of battery capacity. Polymerization is a useful and effective method of reducing the solubility of materials. Screening for appropriate polymeric components, polymerization methods, attachment models, and attachment groups is a specific way to effectively modulate the electrochemical properties and molecular configuration of the polymer chains.
p-type multi-electron active centers such as dihydrophenazine (PZ), phenothiazine (PTZ), phenoxazine (PXZ), diphenyldihydrophenazine (DPPZ), and the like, have attracted attention as active centers of expectable high redox potentials. Among them, PZ and its derivatives DPPZ have a relatively rigid backbone and relatively high theoretical capacity and two stable and reversible redox plateaus (3.1V to 3.9V vs Li) + /Li). However, while p-type ROMs have been successful in achieving high voltages compared to conventional inorganic electrodes, most p-type ROMs do not provide sufficiently high capacity, typically less than 100mAh g -1 Nor sufficiently high energy density, power density and rate capability. Which makes them difficult to apply as positive electrode materials.
The paper "research on high voltage organic cathode materials based on phenazine oligomers" (royal glasan. Research on high voltage organic cathode materials based on phenazine oligomers [ D ]. University of suzhou, 2019.) discloses a phenazine-based polymer p-DPPZ, the structural formula of which is as follows:
Figure BDA0003254425630000021
although the phenazine-based polymer can solve the problem of dissolution of organic materials, the phenazine-based polymer still has difficulty in providing high capacity for an electrode, and when the charge-discharge rate is 1C, the discharge specific capacity is only 145mAh g -1 And finally stabilized at 130mAh g -1 Left and right.
Disclosure of Invention
In order to solve the technical problems, the invention provides a self-crosslinking cross-shaped organic cathode material and a preparation method and application thereof. The organic anode material provided by the invention can enable the metal ion battery to have higher specific capacity and realize high voltage, so that the metal ion battery has higher energy density, power density and rate capability.
The specific technical scheme of the invention is as follows:
in a first aspect, the present invention provides a self-crosslinking cross-shaped organic positive electrode material, which has a structural formula:
Figure BDA0003254425630000022
wherein R1 to R12 are the same or different and are independently selected from-H, -CN, -F, -Cl, -Br and-CH 3 -Et, -nPr, -iPr, -nBu, -tBu, -OMe, -OEt, -OiPr, -OtBu, -Ph, -Tol and-PhOMe.
The organic anode material directly couples and connects p-type rigid active center dihydrophenazine and another p-type rigid active center diphenylphenazine unit. The torsion angle caused by steric hindrance between adjacent monomers is enhanced to be close to 90 degrees through the rigidity of the unit skeleton, so that the following two effects are generated:
(1) increasing the twist angle between rigid adjacent monomers results in non-planar and criss-crossed polymer chains, which can effectively suppress pi-pi accumulation of aromatic polymer chains. This particular cruciform structure facilitates the formation of voids that promote the diffusion efficiency and transport of charge carriers between polymer chains.
(2) The larger torsion angle between the monomer units effectively controls the delocalization of the active center monomer near the monomer, which is beneficial to avoiding larger voltage drop and improving the stability of the polymer.
Through the mode, the organic cathode material has higher charge-discharge voltage, specific capacity, energy density, power density, cycling stability and excellent rate performance.
Furthermore, the type of direct linking employed in the present invention, using rigid redox active fragment units as polymer bridging groups, allows for a reduction in the average molecular weight of the individual active centers and an increase in the theoretical capacity of the final polymeric material.
Moreover, experiments prove that the conversion mechanism of the organic cathode material is not limited by factors such as the number, the type and the particle size of charge carriers, and when the organic cathode material is applied to different types of metal ion batteries such as lithium ion batteries and sodium ion batteries, the organic cathode material can endow the batteries with higher energy density, power density and rate capability.
Preferably, all of R1 to R12 are-H.
In a second aspect, the invention provides a preparation method of the organic cathode material, which comprises the following steps:
(1) 4-bromo-2-fluoro-1-iodobenzene and aniline are used as raw materials to carry out Buchwald-Hartwig reaction to prepare 4-bromo-2-fluoro-N-phenylaniline;
(2) Carrying out C-F amination reaction on 4-bromo-2-fluoro-N-phenylaniline serving as a raw material to prepare 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine;
(3) Taking 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine and 5, 10-dihydrophenazine as monomers, and carrying out Buchwald-Hartwig reaction to prepare the self-crosslinking cross-shaped organic anode material.
Preferably, the specific process of step (1) is as follows: preparing 4-bromo-2-fluoro-1-iodobenzene, aniline, tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl, sodium tert-butoxide and a solvent I into a mixed system I, stirring for 22-24 h at 45-55 ℃ under the condition of reflux condensation, and separating the product to obtain 4-bromo-2-fluoro-N-phenylaniline.
Further, in the step (1), the specific process for preparing the mixed system I from 4-bromo-2-fluoro-1-iodobenzene, aniline, tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl, sodium tert-butoxide and toluene is as follows: removing oxygen from aniline, tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl and sodium tert-butoxide to prepare a mixture I; adding toluene into the mixture I at the temperature of 20-30 ℃ in the inert gas component, removing oxygen, and then adding 4-bromo-2-fluoro-1-iodobenzene to prepare a mixed system I.
Further, in the step (1), the molar ratio of the 4-bromo-2-fluoro-1-iodobenzene to the aniline is 1.3-2.0.
Further, in the step (1), the molar ratio of the 4-bromo-2-fluoro-1-iodobenzene, the tris (dibenzylideneacetone) dipalladium and the 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl is 1.
Further, in the step (1), the molar ratio of the 4-bromo-2-fluoro-1-iodobenzene to the sodium tert-butoxide is 1.5-2.0.
Preferably, the specific process of step (2) is as follows: preparing 4-bromo-2-fluoro-N-phenylaniline, ethyl magnesium bromide, ferrous chloride, 1, 2-dibromoethane and a solvent II into a mixed system II, stirring for 10-14 h at 90-110 ℃ in an inert gas atmosphere and under the reflux condensation condition, and separating a product to obtain 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine.
Further, in the step (2), the specific process for preparing the mixed system II from the 4-bromo-2-fluoro-N-phenylaniline, the ethyl magnesium bromide, the ferrous chloride, the 1, 2-dibromoethane and the solvent II is as follows: adding ethyl magnesium bromide ether solution into a mixture of 4-bromo-2-fluoro-N-phenylaniline and ether at the temperature of 0-5 ℃, stirring for 10-15 min at the temperature of 20-30 ℃, and removing the ether to obtain a mixture II; and adding ferrous chloride, 1, 2-dibromoethane and a solvent II into the mixture II to prepare a mixed system II.
Further, in the step (2), the molar ratio of the 4-bromo-2-fluoro-N-phenylaniline, the ethyl magnesium bromide, the ferrous chloride and the 1, 2-dibromoethane is 1.
Preferably, the specific process of step (3) is as follows: removing oxygen from 5, 10-dihydrophenazine, 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine, palladium acetate, 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl, sodium tert-butoxide and a solvent III to prepare a mixed system III, stirring at 115-125 ℃ for 20-26 h under reflux condensation conditions, then heating to 135-145 ℃ and stirring for 10-14 h, finally adding bromobenzene to perform end capping reaction for 5-6 h, and separating a product to obtain the self-crosslinking crisscross organic anode material.
Further, in the step (3), the molar ratio of the 5, 10-dihydrophenazine to the 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine is 1.
Further, in the step (3), the molar ratio of the 5, 10-dihydrophenazine to the palladium acetate to the 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl is 1.
Further, in the step (3), the molar ratio of the 5, 10-dihydrophenazine to the sodium tert-butoxide is 1.
Preferably, in the step (3), the preparation method of the 5, 10-dihydrophenazine includes the following steps: mixing phenazine and ethanol, removing oxygen, adding sodium disulfite solution, stirring at 80-90 deg.C for 2-4 h under reflux condensation condition, and separating to obtain 5, 10-dihydrophenazine.
In a third aspect, the present invention provides a battery positive electrode comprising the organic positive electrode material.
Preferably, the battery positive electrode further comprises a conductive agent, a binder and a current collector aluminum foil.
In a fourth aspect, the invention provides a metal-ion battery employing the battery positive electrode.
Preferably, the metal ion battery is a lithium ion battery or a sodium ion battery.
Compared with the prior art, the invention has the following advantages:
(1) In the organic anode material, a torsion angle close to 90 degrees is formed between two adjacent active monomers, so that the battery can meet higher specific capacity and realize high voltage, and the battery is endowed with higher energy density, power density and rate capability;
(2) 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 has application prospects in different metal ion batteries.
Drawings
Fig. 1 is a schematic structural view of an organic cathode material of the present invention.
FIG. 2 is a schematic diagram of a possible stacking mode of the organic cathode material and the shuttling of lithium ions in the gap according to the present invention; wherein the ball and stick represent molecular models and the open arrow represents the shuttered lithium ion.
Fig. 3 is a schematic diagram of a synthetic route of the organic cathode material of the present invention.
FIG. 4 is a NMR chart of 4-bromo-2-fluoro-N-phenylaniline obtained in example 1.
FIG. 5 is a mass spectrum of 4-bromo-2-fluoro-N-phenylaniline obtained in example 1.
FIG. 6 is a NMR chart of 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine obtained in example 1.
FIG. 7 is a mass spectrum of 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine obtained in example 1.
Fig. 8 is a mass spectrum of the organic cathode material obtained in example 1.
Fig. 9 is a scanning electron micrograph of the organic cathode material obtained in example 1.
FIG. 10 shows dihydrophenazine (PZ), br obtained in example 1 2 -uv absorption spectra of DPPZ and p-PZ; wherein, the triangle represents PZ, and the box represents Br 2 DPPZ, the circles represent the polymers p-PZ.
Fig. 11 is a powder diffraction XRD pattern of the organic cathode material obtained in example 1.
Fig. 12 is a thermogravimetric analysis TGA plot of the organic cathode material obtained in example 1; wherein the circles represent testing under a nitrogen atmosphere and the boxes represent testing under an air atmosphere.
Fig. 13 is a differential scanning calorimetry, DSC, analysis of the organic cathode material obtained in example 1.
Fig. 14 is a cyclic voltammetry test chart of a lithium ion battery using p-PZ as a positive electrode material in application example 1.
Fig. 15 is a charge-discharge curve at 0.5C rate of a lithium ion battery using p-PZ as a positive electrode material in application example 1; where the circle represents the first turn and the box represents the 800 th turn.
Fig. 16 is a charge-discharge long cycle diagram at a magnification of 0.5C of a lithium ion battery using p-PZ as a positive electrode material in application example 1; wherein, the circle represents the charging specific capacity, the triangle represents the discharging specific capacity, the five-pointed star represents the coulombic efficiency, and the cross represents the energy efficiency.
FIG. 17 is a charge-discharge curve at a rate of 1 to 10C for a lithium ion battery using p-PZ as a positive electrode material in application example 1; wherein, the circle represents the charging specific capacity, the triangle represents the discharging specific capacity, and the square frame represents the coulombic efficiency.
Fig. 18 is a graph comparing the energy density and the power density at different rates of the lithium ion battery using p-PZ and p-DPPZ as the positive electrode materials in application example 1. Wherein the circles represent p-PZ and the triangles represent p-DPPZ.
Fig. 19 is a charge/discharge curve at a 2C rate of the sodium ion battery in application example 2.
Fig. 20 is a charge-discharge long cycle diagram at a 2C rate of the sodium ion battery in application example 2; wherein the circle represents the first turn and the triangle represents the 400 th turn.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A self-crosslinking cross-shaped organic anode material has a structural formula as follows:
Figure BDA0003254425630000061
wherein R1 to R12 are the same or different and are independently selected from-H, -CN, -F, -Cl, -Br and-CH 3 -Et, -nPr, -iPr, -nBu, -tBu, -OMe, -OEt, -OiPr, -OtBu, -Ph, -Tol and-PhOMe.
The structure of the organic cathode material is shown in fig. 1, and the possible stacking manner and the manner of lithium ion shuttling in the gap are shown in fig. 2.
When all of R1-R12 are-H, the synthesis route of the organic cathode material is shown in FIG. 3, and the method comprises the following steps:
(1) Preparation of 4-bromo-2-fluoro-N-phenylaniline:
removing oxygen from aniline, tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl and sodium tert-butoxide to prepare a mixture I; adding toluene into the mixture I at the temperature of 20-30 ℃ in the inert gas component, removing oxygen, and then adding 4-bromo-2-fluoro-1-iodobenzene to prepare a mixed system I. The molar ratio of the 4-bromo-2-fluoro-1-iodobenzene, the aniline, the tris (dibenzylideneacetone) dipalladium, the 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl and the sodium tert-butoxide is 1.3-2.0. And (3) stirring the mixed system I for 22-24 h at the temperature of 45-55 ℃ under the reflux condensation condition, and separating a product to obtain the 4-bromo-2-fluoro-N-phenylaniline.
(2) Preparation of 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine (Br) 2 -DPPZ)：
Adding ethyl magnesium bromide ether solution into a mixture of 4-bromo-2-fluoro-N-phenylaniline and ether at the temperature of 0-5 ℃, stirring for 10-15 min at the temperature of 20-30 ℃, and removing the ether to obtain a mixture II; and adding ferrous chloride, 1, 2-dibromoethane and a solvent II into the mixture II to prepare a mixed system II. The molar ratio of the 4-bromo-2-fluoro-N-phenylaniline, the ethyl magnesium bromide, the ferrous chloride and the 1, 2-dibromoethane is 1. And stirring the mixed system II for 10-14 h at 90-110 ℃ in an inert gas atmosphere and under the reflux condensation condition, and separating a product to obtain the 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine.
(3) Preparing an organic positive electrode material (p-PZ):
removing oxygen from 5, 10-dihydrophenazine, 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine, palladium acetate, 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl, sodium tert-butoxide and solvent III to obtain a mixed system III. The molar ratio of the 5, 10-dihydrophenazine, the 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine, the palladium acetate, the 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl and the sodium tert-butoxide is 1. And (3) stirring the mixed system III for 20-26 h at 115-125 ℃ in a reflux condensation condition, then heating to 135-145 ℃ and stirring for 10-14 h, finally adding bromobenzene to carry out end-capping reaction for 5-6 h, and separating a product to obtain the self-crosslinking cross-shaped organic anode material.
A battery positive electrode containing the organic positive electrode material.
A metal-ion battery using the battery positive electrode.
Example 1
A self-crosslinking cross-shaped organic anode material has a structural formula as follows:
Figure BDA0003254425630000071
wherein, R1-R12 are all-H.
The preparation method of the organic cathode material comprises the following steps:
(1) Preparation of 4-bromo-2-fluoro-N-phenylaniline:
aniline (2.81g, 30mmol), tris (dibenzylideneacetone) dipalladium (0) (549.4 mg,0.6 mmol), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (492.6 mg,1.2 mmol) and sodium tert-butoxide (3.36g, 35mmol) were added to a 250mL flask, and mixture I was prepared by bubbling nitrogen at 25 ℃ for 30 minutes; toluene (40 mL) was added to the mixture I under nitrogen atmosphere at 25 ℃ and after 3 times of purging, 4-bromo-2-fluoro-1-iodobenzene (5.99g, 20mmol) was added to prepare a mixed system I. The mixed system I was stirred at 50 ℃ for 23h under reflux condensation conditions and then cooled to 25 ℃. The resulting crude product was purified by column chromatography on neutral alumina (PE/DCM 20.
The obtained 4-bromo-2-fluoro-N-phenylaniline was characterized by nmr hydrogen spectrum and mass spectrum, and the results are shown in fig. 4 and fig. 5, respectively.
(2) Preparation of 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine (Br) 2 -DPPZ)：
Ethyl magnesium bromide in ether (1mL, 2.97mol/L) was added to a mixture of 4-bromo-2-fluoro-N-phenylaniline (791.0 mg,29.1 mmol) and ether (1.0 mL) at 0 deg.C, and after stirring for 10min at 25 deg.C, the ether was removed in vacuo to give mixture II; ferrous chloride (20.0 mg, 0.16mmol), 1, 2-dibromoethane (1.11g, 5.93mmol), and toluene (10 mL) were added to mixture II to prepare mixed system II. The mixed system II was stirred at 100 ℃ for 12h under nitrogen atmosphere and reflux condensation conditions and then cooled to 25 ℃. The resulting crude product was recrystallized from a mixed solvent of DCM and MeOH to give a yellow solid, i.e., 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine (Br) 2 -DPPZ)。
The obtained 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine was characterized by nuclear magnetic resonance hydrogen spectroscopy and mass spectrometry, and the results are shown in fig. 6 and fig. 7, respectively.
(3) Preparation of 5, 10-dihydrophenazine:
phenazine (10.0 g,55.6 mmol) and ethanol (15 mL) were placed in a 100mL flask and degassed. Then, sodium dithionite (100.0 g,574.4 mmol) dissolved in deionized water (20 mL) was added to the flask to prepare a reaction mixture. The reaction mixture was stirred with a reflux condenser at 80 ℃ for 3.5 hours under nitrogen. After cooling to room temperature, the reaction solution was filtered, and the obtained solid was washed with deionized water (100 mL. Times.3) and dried under vacuum at 60 ℃ to give a pale yellow-green solid (9.0 g, yield 90%) which was 5, 10-dihydrophenazine.
(4) Preparing an organic positive electrode material (p-PZ):
degassing 5, 10-dihydrophenazine (182mg, 1mmol) and 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine (492mg, 1mmol) in anhydrous xylene (25 mL) to give solution A; simultaneously, palladium acetate (22mg, 10mol%), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (48mg, 20mol%) and sodium tert-butoxide (360mg, 2.5mmol) were degassed in anhydrous xylene (25 mL) to obtain a solution B. And adding the solution B into the solution A, and removing oxygen through three freezing pumps and unfreezing circulation to obtain a mixed system III. And (3) stirring the mixed system III for 24 hours at 120 ℃ in a nitrogen atmosphere and under the reflux condensation condition, then heating to 140 ℃, stirring for 12 hours, and finally adding 0.5mL of bromobenzene to carry out end-capping reaction for 5 hours. After cooling to room temperature, the mixture was filtered. With copious amounts of hot o-xylene, dichloromethane (DCM), meOH and H 2 O wash the solid part (crude product). The solubility of p-PZ was very poor, therefore, the product was dispersed in DCM by mortar and sonication, then filtered and passed through DCM, THF, et 3 N, meOH and H 2 And (4) washing. After repeating this procedure five times, the product was purified by Physical Vapor Deposition (PVD) instrument at 350 ℃ under vacuum for 12h to remove small molecular weight products, yielding a brownish black solid (363.5 mg), and an organic positive electrode material (p-PZ) that is a self-crosslinking cross.
Mass spectrum characterization was performed on the obtained p-PZ, and the results are shown in FIG. 8, in which the degree of polymerization was mainly 2 to 4.
The morphology of the polymer p-PZ sample was observed with a Scanning Electron Microscope (SEM), as shown in FIG. 9. The purified polymer p-PZ material showed irregular blocky particles ranging in size from 1 to 5 μm.
The solubility of the polymer material in the electrolyte EC/DEC of the lithium ion battery according to the example of the invention was characterized by uv absorption spectroscopy. As is evident from the UV absorption spectrum (FIG. 10), 10 -5 M Polymer monomer Br 2 The absorption peaks of the EC/DEC solutions of-DPPZ and PZ are clearly visible at approximately 379 and 364 nm. The absorption peak of the p-PZ saturated EC/DEC solution is almost invisible, which shows that the solubility of the p-PZ is extremely low, thereby being beneficial to the application of the battery and avoiding the capacity attenuation caused by the dissolution of the active material in the electrolyte.
Powder X-ray diffraction (XRD) analysis of the crystalline structure of polymer p-PZ showed two broad diffraction peaks in the small and wide angle regions, respectively, as shown in fig. 11. 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. Whereas 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 were performed on a METTLER TA instrument at a heating rate of 10 ℃ per minute under a stream of nitrogen or air. In FIGS. 12 and 13, the results show that p-PZ decomposed at about 430 ℃ under an air atmosphere; whereas under nitrogen atmosphere, the p-PZ decomposes at about 490 deg.C. The p-PZ does not melt or change phase in the temperature range of 0-300 ℃, namely the requirement of battery preparation is met.
Example 2
A self-crosslinking cross-shaped organic anode material has a structural formula as follows:
Figure BDA0003254425630000091
wherein R1 to R12 are all-H.
The preparation method of the organic cathode material comprises the following steps:
(1) Preparation of 4-bromo-2-fluoro-N-phenylaniline:
aniline (2.44g, 26mmol), tris (dibenzylideneacetone) dipalladium (0) (732.5mg, 0.8mmol), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (656.8mg, 1.6mmol) and sodium tert-butoxide (2.88g, 30mmo) were put in a 250mL flask and purged with nitrogen at 25 ℃ for 30 minutes to prepare a mixture I; toluene (40 mL) was added to the mixture I under nitrogen atmosphere at 25 ℃ and after 3 times of purging, 4-bromo-2-fluoro-1-iodobenzene (5.99g, 20mmol) was added to prepare a mixed system I. The mixed system I was stirred at 45 ℃ for 24h under reflux condensation conditions and then cooled to 25 ℃. The resulting crude product was purified by column chromatography on neutral alumina (PE/ DCM 20, 1, 10.
(2) Preparation of 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine (Br) 2 -DPPZ)：
Ethyl magnesium bromide in ether (1ml, 4.36m, 0.11mmol) was added to a mixture of 4-bromo-2-fluoro-N-phenylaniline (774.3mg, 29.1mmol) and ether (1.0 mL) at 3 ℃, and after stirring for 15min at 20 ℃, the ether was removed in vacuo to give mixture II; ferrous chloride (36.3mg, 0.29mmol), 1, 2-dibromoethane (1.36g, 7.27mmol) and toluene (10 mL) were added to mixture II to produce mixed system II. The mixed system II was stirred at 90 ℃ for 14h under nitrogen atmosphere and under reflux condensation conditions and then cooled to 25 ℃. The resulting crude product was recrystallized from a mixed solvent of DCM and MeOH to give a yellow solid, i.e., 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine (Br) 2 -DPPZ)。
(3) Preparation of 5, 10-dihydrophenazine:
phenazine (10.0 g,55.6 mmol) and ethanol (15 mL) were placed in a 100mL flask for degassing. Then, sodium dithionite (100.0 g,574.4 mmol) dissolved in deionized water (20 mL) was added to the flask to prepare a reaction mixture. The reaction mixture was stirred with a reflux condenser at 80 ℃ for 3.5 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction solution was filtered, and the obtained solid was washed with deionized water (100 mL. Times.3) and dried under vacuum at 60 ℃ to give a pale yellow-green solid (9.0 g, yield 90%) which was 5, 10-dihydrophenazine.
(4) Preparation of organic cathode material (p-PZ):
degassing 5, 10-dihydrophenazine (182mg, 1mmol) and 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine (345mg, 0.7mmol) in anhydrous xylene (25 mL) to give solution A; palladium acetate (22mg, 10mol%), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (72mg, 20mol%) and sodium tert-butoxide (192mg, 20mmol) were degassed in anhydrous xylene (25 mL) at the same time to obtain a solution B. And adding the solution B into the solution A, and removing oxygen through three freezing pumps and unfreezing circulation to obtain a mixed system III. And (3) stirring the mixed system III for 26h at 115 ℃ in a nitrogen atmosphere under reflux condensation conditions, then heating to 135 ℃, stirring for 14h, and finally adding 0.5mL of bromobenzene to carry out end-capping reaction for 5.5h. After cooling to room temperature, the mixture was filtered. With copious amounts of hot o-xylene, dichloromethane (DCM), meOH and H 2 O wash the solid part (crude product). The solubility of p-PZ was very poor, therefore, the product was dispersed in DCM by mortar and sonication, then filtered and passed through DCM, THF, et 3 N, meOH and H 2 And (4) washing. After repeating this procedure five times, the product was purified by Physical Vapor Deposition (PVD) instrument at 350 ℃ under vacuum for 12h to remove small molecular weight products, yielding a brownish black solid, and an organic positive electrode material (p-PZ) of self-crosslinking cross shape.
Example 3
A self-crosslinking cross-shaped organic anode material has a structural formula as follows:
Figure BDA0003254425630000111
wherein R1 to R12 are all-H.
The preparation method of the organic cathode material comprises the following steps:
(1) Preparation of 4-bromo-2-fluoro-N-phenylaniline:
aniline (3.75g, 40mmol), tris (dibenzylideneacetone) dipalladium (0) (915.7mg, 1mmol), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (812mg, 2mmol) and sodium tert-butoxide (3.84g, 40mmol) were put in a 250mL flask, and a mixture I was prepared by introducing nitrogen gas and blowing at 25 ℃ for 30 minutes; toluene (40 mL) was added to the mixture I under nitrogen atmosphere at 25 ℃ and after 3 times of purging, 4-bromo-2-fluoro-1-iodobenzene (5.99g, 20mmol) was added to prepare a mixed system I. The mixture I was stirred at 55 ℃ for 22h under reflux condensation conditions and then cooled to 25 ℃. The resulting crude product was purified by column chromatography on neutral alumina (PE/ DCM 20, 1, 10.
(2) Preparation of 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine (Br) 2 -DPPZ)：
A solution of ethyl magnesium bromide in diethyl ether (1mL, 3.78M, 0.116mmol) was added to a mixture of 4-bromo-2-fluoro-N-phenylaniline (791.0 mg, 29.1mmol) and diethyl ether (1.0 mL) at 5 deg.C, and after stirring at 30 deg.C for 10min, the diethyl ether was removed in vacuo to give mixture II; ferrous chloride (53.75mg, 0.43mmol), 1, 2-dibromoethane (1.63g, 8.73mmol) and toluene (10 mL) were added to mixture II to prepare mixed system II. The mixed system II was stirred at 110 ℃ for 10h under nitrogen atmosphere and reflux condensation conditions and then cooled to 25 ℃. The resulting crude product was recrystallized from a mixed solvent of DCM and MeOH to give a yellow solid, i.e., 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine (Br) 2 -DPPZ)。
(3) Preparation of 5, 10-dihydrophenazine:
phenazine (10.0 g,55.6 mmol) and ethanol (15 mL) were placed in a 100mL flask and degassed. Then, sodium dithionite (100.0 g,574.4 mmol) dissolved in deionized water (20 mL) was added to the flask to prepare a reaction mixture. The reaction mixture was stirred with a reflux condenser at 80 ℃ for 3.5 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction solution was filtered, and the obtained solid was washed with deionized water (100 mL. Times.3) and dried under vacuum at 60 ℃ to give a pale yellow-green solid (9.0 g, yield 90%) which was 5, 10-dihydrophenazine.
(4) Preparation of organic cathode material (p-PZ):
degassing 5, 10-dihydrophenazine (182mg, 1mmol) and 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine (640mg, 1.3mmol) in anhydrous xylene (25 mL) to obtain a solution A; palladium acetate (44mg, 10mol%), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (96mg, 20mol%) and sodium tert-butoxide (4322mg, 3mmol) were degassed in anhydrous xylene (25 mL) at the same time to obtain a solution B. And adding the solution B into the solution A, and removing oxygen through three freezing pumps and unfreezing circulation to obtain a mixed system III. And (3) stirring the mixed system III for 20 hours at 125 ℃ in a nitrogen atmosphere under reflux condensation conditions, then heating to 145 ℃, stirring for 10 hours, and finally adding 0.5mL of bromobenzene to carry out end-capping reaction for 6 hours. After cooling to room temperature, the mixture was filtered. With copious amounts of hot o-xylene, dichloromethane (DCM), meOH, and H 2 O wash the solid part (crude product). The solubility of p-PZ was very poor, therefore, the product was dispersed in DCM by mortar and sonication, then filtered and passed through DCM, THF, et 3 N, meOH and H 2 And (4) washing. After repeating this process five times, the product was purified by Physical Vapor Deposition (PVD) apparatus at 350 ℃ under vacuum for 12h to remove small molecular weight products, resulting in a dark brown solid, and an organic positive electrode material (p-PZ) that is a self-crosslinking cross.
Comparative example 1
The polymer p-DPPZ was prepared according to the synthesis method in the thesis "investigation of high voltage organic cathode materials based on phenazine oligomers".
Application example 1: lithium ion battery
Using P-PZ prepared in example 1 and P-DPPZ prepared in comparative example 1 as positive electrode materials, respectively, the positive electrode material, super P and polyvinylidene fluoride were mixed in a weight ratio of 7. The slurry was then cast on an aluminum foil 50 μm thick, dried in vacuum at 60 ℃ for 12h, at 10MPa cm -2 Is pressed under pressure and cut into disks having a diameter of 10 mm. Batteries were placed in a glove box (H) using standard CR2032 coin cell batteries 2 O and O 2 Concentration of<1 ppm) in which a metallic lithium plate is used as a negative electrode, celgard 2500 as separator, 1M LiPF 6 EC/DEC (v: v 1).
FIG. 14 is a cyclic voltammetry test chart of a lithium ion battery with p-PZ as the positive electrode and a lithium plate as the negative electrode. For Li + The polymer p-PZ gave an average high cell discharge voltage of 3.6V/Li.
Fig. 15 is a charge-discharge curve at 1C rate of a lithium ion battery using a polymer p-PZ as a positive electrode material. The initial discharge capacity of the p-PZ at 1C is up to 198mAh/g, which is close to the theoretical specific capacity of 209mAh/g, and the p-PZ has the advantages that all four active centers participate in the electrochemical reaction (namely, the utilization rate is close to 100%).
Fig. 16 is a long cycle diagram of charge and discharge at 1C rate of a lithium ion battery using a polymer p-PZ as a positive electrode material. The cycling of p-PZ was stable and the relatively low coulombic efficiency in the first few cycles was due to the formation of a solid electrolyte interface layer. During the subsequent 800 charge/discharge cycles, the Coulombic Efficiency (CE) of the p-PZ was close to 100%, and the capacity retention rate after 800 cycles was as high as 92%.
FIG. 17 is a graph of the rate cycling of lithium ion batteries using polymer p-PZ as the positive electrode material at different rates. The p-PZ-based electrode showed high rate performance, high energy density and high power density, with average capacities at 1,2, 5 and 10C of 153, 135, 116 and 63mAh g, respectively -1 . Corresponding power densities up to about 558, 986, 2117 and 2300W kg -1 The energy density reaches 558, 493, 423 and 230Wh kg respectively -1 。
FIG. 18 is a graph comparing energy density and power density at different rates for lithium ion batteries using p-PZ and p-DPPZ as positive electrode materials, respectively. Under the test conditions of 1,2 and 5C, the power density of the polymer p-PZ anode is 558, 986 and 2117W kg -1 The energy density is 558, 493, 423Wh kg -1 The power density of the polymer p-DPPZ positive electrode is 490, 770 and 1137W kg -1 Energy density was 490, 350, 227Wh kg -1 . Under different multiplying powers, the power density and the energy density of the polymer p-PZ positive electrode are higher than those of the polymer p-DPPZ positive electrode, and the performance is more excellent.
Application example 2: sodium ion battery
The organic cathode material (P-PZ) prepared in example 1, super P and polyvinylidene fluoride were mixed in N-methyl-2-pyrrolidone (anhydrous) at a weight ratio of 7. The slurry was then cast on an aluminum foil 50 μm thick, dried in vacuum at 60 ℃ for 12h, at 10MPa cm -2 Is pressed under pressure and cut into disks having a diameter of 10 mm. Batteries were placed 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. 19 is a charge-discharge curve at 2C rate for a sodium ion battery using the polymer p-PZ as the positive electrode material according to the example of the present invention. The p-PZ based electrode showed 157mAh g at a rate of 2C in the first cycle -1 The specific capacity of the lithium ion battery is equivalent to that of the lithium ion battery.
Fig. 20 is a charge-discharge long cycle diagram at 2C rate for a sodium ion battery using the polymer p-PZ as the positive electrode material shown in the example of the present invention. Since sodium has a larger ion radius than lithium, sodium ion batteries have a faster capacity fade than lithium ion batteries. However, the polymer p-PZ still has a specific capacity retention rate of 67% after 400 cycles, and is much more stable than the previously reported sodium ion battery using organic matter as an electrode.
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 self-crosslinking cross-shaped organic anode material is characterized in that the structural formula is as follows:
Figure FDA0004077778650000011
wherein R1-R12 are-H; n =2 to 4.
2. A method for preparing the organic cathode material according to claim 1, comprising the steps of:
(1) Taking 4-bromo-2-fluoro-1-iodobenzene and aniline as raw materials, and carrying out Buchwald-Hartwig reaction to obtain 4-bromo-2-fluoro-N-phenylaniline;
(2) Carrying out C-F amination reaction on 4-bromo-2-fluoro-N-phenylaniline serving as a raw material to prepare 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine;
(3) Taking 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine and 5, 10-dihydrophenazine as monomers, and carrying out Buchwald-Hartwig reaction to prepare the self-crosslinking cross-shaped organic anode material.
3. The method of claim 2, wherein the specific process of step (1) is as follows: preparing 4-bromo-2-fluoro-1-iodobenzene, aniline, tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl, sodium tert-butoxide and a solvent I into a mixed system I, stirring for 22-24 h at 45-55 ℃ under the condition of reflux condensation, and separating the product to obtain 4-bromo-2-fluoro-N-phenylaniline.
4. The method according to claim 2, wherein the specific process of step (2) is as follows: preparing 4-bromo-2-fluoro-N-phenylaniline, ethyl magnesium bromide, ferrous chloride, 1, 2-dibromoethane and a solvent II into a mixed system II, stirring for 10-14 h at 90-110 ℃ in an inert gas atmosphere and under the reflux condensation condition, and separating a product to obtain 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine.
5. The method according to claim 4, wherein in the step (2), the mixed system II comprising 4-bromo-2-fluoro-N-phenylaniline, ethylmagnesium bromide, iron (II) chloride, 1, 2-dibromoethane and the solvent II is prepared by the following steps: adding ethyl magnesium bromide ether solution into a mixture of 4-bromo-2-fluoro-N-phenylaniline and ether at the temperature of 0-5 ℃, stirring for 10-15 min at the temperature of 20-30 ℃, and removing the ether to obtain a mixture II; and adding ferrous chloride, 1, 2-dibromoethane and a solvent II into the mixture II to prepare a mixed system II.
6. The production method according to claim 4 or 5, wherein in the step (2), the molar ratio of the 4-bromo-2-fluoro-N-phenylaniline, the ethylmagnesium bromide, the ferrous chloride and the 1, 2-dibromoethane is 1.
7. The method according to claim 2, wherein the specific process of step (3) is as follows: removing oxygen from 5, 10-dihydrophenazine, 2, 7-dibromo-5, 10-diphenyl-5, 10-dihydrophenazine, palladium acetate, 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl, sodium tert-butoxide and a solvent III to prepare a mixed system III, firstly stirring for 20-26 h at 115-125 ℃ in a reflux condensation condition, then heating to 135-145 ℃ and stirring for 10-14 h, finally adding bromobenzene for end capping reaction for 5-6 h, and separating a product to obtain the self-crosslinking cross-shaped organic anode material.
8. A positive electrode for a battery comprising the organic positive electrode material according to claim 1.
9. A metal-ion battery using the positive electrode of claim 8.
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