CN110767469A - Polymer mixture for organic electrode material, preparation method and application thereof - Google Patents

Polymer mixture for organic electrode material, preparation method and application thereof Download PDF

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CN110767469A
CN110767469A CN201910700120.5A CN201910700120A CN110767469A CN 110767469 A CN110767469 A CN 110767469A CN 201910700120 A CN201910700120 A CN 201910700120A CN 110767469 A CN110767469 A CN 110767469A
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electrode material
polymer mixture
polymer
organic electrode
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CN110767469B (en
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李辰
刘志宏
段若蒙
田禾
魏文山
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Dongguan University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H01M10/24—Alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/606—Polymers containing aromatic main chain polymers
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    • 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
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Abstract

The application provides a polymer mixture of an organic electrode material, the polymer is a conjugated polymer polymerized by double bonds, compared with a polymer polymerized by single bonds, the polymer has narrower energy gap and higher conductivity, and the solubility can be effectively reduced by a conjugated system polymerized by double bonds, so that the polymer is insoluble in most organic solvents and can stably exist in electrolyte. In addition, the application also provides a preparation method and application of the polymer mixture.

Description

Polymer mixture for organic electrode material, preparation method and application thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to a polymer mixture for an organic electrode material, a preparation method and application thereof.
Background
The battery is used as an energy source, can provide stable voltage and stable current and stably supply power for a long time, has simple structure, convenient carrying, simple and easy charging and discharging, is not influenced by external climate and temperature, has stable and reliable performance, and plays a great role in various aspects of modern social life. In order to meet the demand of the power tool, a battery system having a higher energy density, a discharge performance of a large current, a good cycle performance, and a long life is becoming a trend. The battery comprises electrolyte, diaphragm material, binder and anode and cathode materials, the performance of the materials can affect the performance of the battery, especially the performance of the anode and cathode materials has great influence on the performance of the battery, and the cost directly determines the cost of the battery.
Organic compound raw materials are widely used in various industries because of their wide variety, low price and easy availability. Among them, some organic compounds having conductive properties, especially small molecules or high molecular compounds containing sulfur, radicals, carbonyl groups, nitrogen, are increasingly used in alkali metal batteries and supercapacitors. Pyrimidines, imides, graphenes, and conductive polymers have all been demonstrated to be excellent positive or negative electrode materials.
However, the current application of organic compounds as electrode materials in chargeable and dischargeable batteries and capacitors has the following problems: (1) most of organic micromolecules have good solubility and can be slowly dissolved in electrolyte, so that the battery has poor cycle capacity; (2) most organic small molecules and macromolecules have low conductivity, and the conductivity needs to be improved by doping with other compounds to change the structure of the molecules, but the stability of the doped compounds is reduced, so that the service life of the battery is greatly reduced; (3) when organic molecules are used as electrodes, a large amount of conductive graphite or other conductors are required to be matched and combined with a binder, so that the organic molecules are used as electrodes in batteries with low efficiency.
Therefore, it is important to develop an organic compound which has high conductivity without doping, low solubility, and can be stably present in an electrolyte for a long time, and to produce an energy storage device having a long lifetime, a high cycle number, and a large capacity.
Disclosure of Invention
Based on this, there is a need to provide a polymer mixture for an organic electrode material having high conductivity, low solubility, insolubility in most organic solvents, and stability in an electrolyte.
A polymer mixture for an organic electrode material, the polymer comprising structural units according to formula (I):
Figure BDA0002150558070000021
wherein,
Figure BDA0002150558070000024
represents a connecting bond to an adjacent structural unit;
Figure BDA0002150558070000022
represents a residue of a conjugated polycyclic aromatic compound attached to the linkage; m is an integer of 2 or more.
In one embodiment, the polymer further comprises a terminal structural unit represented by formula (II):
Figure BDA0002150558070000023
wherein, Y is each independently O or S; m1+ m2 ═ m, and m1 and m2 are integers.
In one embodiment, the conjugated polycyclic aromatic compound residue is one of the following structures:
Figure BDA0002150558070000031
Figure BDA0002150558070000041
wherein R is1、R4、R5Each independently selected from alkyl, alkyl containing hetero atom or aryl with substituent;
R2、R3each independently selected from N, O, S or C, and R2And R3Connected to form a five-membered ring or a six-membered ring;
X1each independently N, P, B or CH;
X2each independently is N or CH.
In addition, the application also provides a preparation method of the polymer mixture for the organic electrode material, and the specific scheme is as follows:
a method for preparing a polymer mixture for an organic electrode material, comprising the steps of:
mixing a conjugated polycyclic aromatic compound containing more than two carbonyl groups with an oxygen-sulfur exchange reagent, heating and refluxing in a high-boiling point solvent for reaction, and separating and purifying after the reaction is finished to obtain a polymer mixture for the organic electrode material, wherein the polymer comprises a structural unit shown as a formula (I):
Figure BDA0002150558070000042
wherein,
Figure BDA0002150558070000044
represents a connecting bond to an adjacent structural unit;
Figure BDA0002150558070000043
represents a residue of a conjugated polycyclic aromatic compound attached to the linkage; m is an integer of 2 or more.
In one embodiment, the polymer further comprises a terminal structural unit represented by formula (II):
Figure BDA0002150558070000051
wherein, Y is each independently O or S; m1+ m2 ═ m, and m1 and m2 are integers.
In one embodiment, the conjugated polycyclic aromatic compound containing two or more carbonyl groups is selected from one of the following compounds:
Figure BDA0002150558070000052
Figure BDA0002150558070000061
wherein R is1、R4、R5Each independently selected from alkyl, alkyl containing hetero atom or aryl with substituent;
R2、R3each independently selected from N, O, S or C, and R2And R3Connected to form a five-membered ring or a six-membered ring;
X1each independently N, P, B or CH;
X2each independently is N or CH.
In one embodiment, the oxygen-sulfur exchange reagent is one or more of lawson's reagent, Davy's reagent, japan's reagent, Belleau's reagent, tetraphosphorus decasulfide, a mixture of hydrogen sulfide and hydrogen chloride, or other polysulfide-containing compounds.
In one embodiment, the high boiling point solvent is a solvent having a boiling point above 160 ℃.
In one embodiment, the high boiling point solvent is one or more of trichlorobenzene, trimethylbenzene, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, dimethylacetamide, N-dimethylpropyleneurea, 1, 3-dimethyl-2-imidazolidinone, quinoline, or diphenyl ether.
In addition, the application also provides an application of the polymer mixture for the organic electrode material in an alkali metal battery or a super capacitor, and the specific scheme is as follows:
use of the polymer mixture for organic electrode material described in any of the above or the polymer mixture for organic electrode material prepared by the preparation method described in any of the above in an alkali metal battery or a supercapacitor.
The polymer mixture for the organic electrode material is a conjugated polymer polymerized by double bonds, has a narrower energy gap and higher conductivity compared with a polymer polymerized by single bonds, can effectively reduce the solubility through a conjugated system polymerized by double bonds, is insoluble in most organic solvents, can stably exist in an electrolyte, is applied to an alkali metal battery or a super capacitor as the organic electrode material, and has excellent cyclic charge and discharge stability.
In addition, the polymer for the organic electrode material is mixed, and the conjugated polycyclic aromatic compound containing more than two carbonyl groups and the oxygen-sulfur exchange reagent are heated and reacted in a high-boiling-point solvent, so that the preparation method is simple and efficient, and has a relatively high application prospect in the field of electrode materials of super capacitors behind alkali metal batteries.
Drawings
FIG. 1 is an SEM image of polymer mixture nanoparticles prepared in example 1 at low magnification;
FIG. 2 is an SEM image of polymer mixture nanoparticles prepared in example 1 at high magnification;
FIG. 3 shows the scanning rate of 0.1mV for the lithium-ion button cell prepared in application example 1-1Cyclic voltammogram;
FIG. 4 shows the current density of 1000mAg for the lithium-ion button cell prepared in application example 1-1Long cycle performance in time;
FIG. 5 shows the scan rate of 0.1mV for the button cell prepared in application example 2-1Cyclic voltammogram;
FIG. 6 shows the current density of 500mAg for the button cell prepared in application example 2-1Long cycle performance in time;
fig. 7 is a first three-cycle discharge voltage curve of the positive electrode of the lithium-sulfur battery prepared in application example 3 at 0.1C;
fig. 8 is a cycle performance curve of the lithium sulfur battery prepared in application example 3.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In this application, "+" denotes a connection site.
An embodiment of a polymer mixture for an organic electrode material includes a structural unit represented by formula (I):
Figure BDA0002150558070000091
wherein,
Figure BDA0002150558070000096
represents a connecting bond to an adjacent structural unit;
Figure BDA0002150558070000092
represents a residue of a conjugated polycyclic aromatic compound linked to a linking bond; m is an integer of 2 or more.
Further, the polymer also comprises a terminal structural unit shown as a formula (II):
Figure BDA0002150558070000093
wherein, Y is each independently O or S; m1+ m2 ═ m, and m1, m2 are integers;
Figure BDA0002150558070000097
and
Figure BDA0002150558070000094
the definition of (A) is as above.
Further, the conjugated polycyclic aromatic compound residue is one of the following structures:
Figure BDA0002150558070000095
Figure BDA0002150558070000101
wherein R is1、R4、R5Each independently selected from alkyl (linear or branched), alkyl containing hetero atom group (such as carbonyl, sulfhydryl, amino, amido, imido, siloxy, halogen, oxy, etc.), or substituted aromatic group (such as benzene, naphthalene, thiophene, furan, pyrrole, pyridine, etc.);
R2、R3each independently selected from N, O, S or C, and R2And R3Connected to form a five-membered ring or a six-membered ring;
X1each independently N, P, B or CH;
X2each independently is N or CH.
Further, the polymer comprises one of the following structural units:
Figure BDA0002150558070000111
Figure BDA0002150558070000112
R1、R4、R5、R2、R3、X1and X2The definition of (A) is as above.
The polymer mixture for the organic electrode material is a conjugated polymer polymerized by double bonds, has a narrower energy gap and higher conductivity compared with a polymer polymerized by single bonds, can effectively reduce the solubility through a conjugated system polymerized by double bonds, is insoluble in most organic solvents, can stably exist in an electrolyte, is applied to an alkali metal battery or a super capacitor as the organic electrode material, and has excellent cyclic charge and discharge stability and higher specific capacity.
The method for preparing the polymer mixture for an organic electrode material according to an embodiment includes the steps of:
mixing a conjugated polycyclic aromatic compound containing more than two carbonyl groups with an oxygen-sulfur exchange reagent, heating and refluxing in a high-boiling point solvent for reaction, and separating and purifying after the reaction is finished to obtain the polymer mixture for the organic electrode material.
Among them, the conjugated polycyclic aromatic compound containing two or more carbonyl groups can be represented as follows:
Figure BDA0002150558070000121
m is an integer of 2 or more.
Further, the conjugated polycyclic aromatic compound containing two or more carbonyl groups is selected from one of the following compounds:
Figure BDA0002150558070000122
Figure BDA0002150558070000131
R1、R4、R5、R2、R3、X1and X2The definition of (A) is as above.
Further, the oxygen sulfur exchange reagent is selected from one or more of lawson's reagent, Davy's reagent, japan's reagent, Belleau's reagent, tetraphosphorus decasulfide, a mixture of hydrogen sulfide and hydrogen chloride, and other polysulfide-containing compounds.
Further, the high boiling point solvent is a solvent having a boiling point of 160 ℃ or higher. Further, the high boiling point solvent is selected from one or more of trichlorobenzene, trimethylbenzene, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), Dimethylacetamide (DMAC), N-Dimethylpropyleneurea (DMPU), 1, 3-dimethyl-2-imidazolidinone (DMI), quinoline, and diphenyl ether.
Further, the separation and purification method comprises the following steps: cooling, filtering, washing and drying.
The preparation method of the polymer mixture for the organic electrode material is obtained by heating and reacting the conjugated polycyclic aromatic compound containing more than two carbonyl groups and the oxygen-sulfur exchange reagent in a high-boiling-point solvent, is simple and efficient, has low cost, and has a relatively high application prospect in the field of electrode materials of super capacitors after alkali metal batteries.
The following are specific examples.
The polymer mixtures for organic electrode materials of all examples were prepared according to the following method, in particular:
as shown in table 1, a conjugated polycyclic aromatic compound containing two or more carbonyl groups, an oxygen-sulfur exchange reagent, and a high boiling point solvent were mixed, heated, refluxed, and stirred until the reaction solution turned black, and cooled, filtered, washed, and dried to obtain a polymer mixture nanoparticle electrode material.
TABLE 1
Figure BDA0002150558070000141
Figure BDA0002150558070000151
Application example 1
Pasting 70 wt.% of the polymer mixture nanoparticles prepared in example 1 (SEM images of the polymer mixture nanoparticles are shown in fig. 1 and 2), 20 wt.% of super P and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
The lithium ion button cell prepared in example 1 was tested, and the results show that: at 100mAg-1The discharge and charge capacities of the lithium-ion button cell prepared in application example 1 are 503mAhg respectively at low current density-1And 494mAhg-1It is shown that the electrode material prepared in example 1 has a high specific capacity, which is higher than that of a commercial graphite anode (372 mAhg)-1) Higher than 50%, even higher than previously reported organic anodes (e.g. ellagic acid 450 mAhg)-1The poly-p-phenylene group is 400mAhg-1)。
In FIG. 3, at 2.23/1.50V and 1.06/0.70V vs. Li/Li+There are two pairs of reversible redox peaks in between. Further, the intensity of the redox peak obtained at 1.06V/0.70V was about four times the intensity of the peak obtained at 2.23V/1.50V. The cycling performance of the nanoparticle negative electrode is shown in fig. 4. Capacity of about 370mAhg after 600 long cycles-1The capacity fade is negligible. Due to early SEI formation and irreversible capacity loss, charge-discharge coulombic efficiency increased from 65% to over 99% over the initial 20 cycles, and then remained fairly stable over subsequent cycles. Unlike other small organic molecules that are easily dissolved in the electrolyte during charge/discharge, the nanoparticles swell only in the non-aqueous electrolyte during charge/discharge and remain adhered to the negative electrode sheet after a long cycle life, so that excellent cycle performance is facilitated.
Application example 2
The polymer mixture nanoparticles prepared in example 1 were used as a negative electrode material for assembling 2032 cells. The 2032 cell was assembled using sodium foil as the counter electrode and 1M NaPF6/EC-DMC as the electrolyte. After 500 cycles of long life, the capacity is from the initial 250mAhg-1Slightly decaying to a final 200mAh g-1The capacity retention rate is 80% or more. In the first 20 cycles, the coulombic efficiency was approaching 100%. These results confirm that the above-mentioned negative electrode also has a better cycle stability performance for sodium ion storage.
The CV curve of the nanoparticles is shown in fig. 5. In the CV curveAt 1.87/1.75V and 0.69/0.31V (vs. Na/Na)+) There are two pairs of reversible redox peaks. Much like the lithium ion/delithiation results in fig. 3, these two pairs of reversible redox reactions are due to the sodium association/dissociation process that occurs at the carbonyl oxygen on the end group and the unsaturated nitrogen of the aromatic ring, respectively. The potential at these peak positions is lower than-0.30V in FIG. 3 because of Na/Na+Potential ratio of Li/Li+0.30V higher. FIG. 6 shows the cycling performance of sodium ion storage at a current density of 500mAg-1 (1.6C). After 500 cycles of long life, the capacity was slightly attenuated from the initial 250mAhg-1 to the final 200 mAhg g-1, with capacity retention above 80%. The first coulombic efficiency was 43%, and the lithium ion/delithiation rate was 65%. This finding indicates a higher initial capacity loss due to SEI formation and side reactions of the sodium metal foil. In the first 20 cycles, the coulombic efficiency was approaching 100%. These results confirm that the negative electrode also has better cycling stability for sodium ion storage.
Application example 3
The polymer mixture nanoparticles prepared in example 1 were used as a positive electrode material for assembling a lithium sulfur battery.
Wherein, fig. 7 is a first three-turn charge-discharge voltage curve of the battery at room temperature and 0.1C. The specific discharge capacity of the battery under different multiplying powers is respectively 910mAh/g, 580mAh/g, 450mAh/g, 400mAh/g and 380mAh/g, and the coulombic efficiency is about 90%.
As can be seen in FIG. 8, the specific discharge capacity of the battery at 0.5C in the first cycle is 800mAh/g, and the capacity is maintained at about 420mAh/g after 80 cycles of cycling. Meanwhile, the coulombic efficiency of the battery is maintained to be about 92%. Multiplying power graphs of the lithium-sulfur batteries at 0.1C, 0.5C, 1C, 2C and 5C respectively.
Application example 4
Pasting 70 wt.% of the polymer mixture nanoparticles prepared in example 4, 20 wt.% of conductive carbon black and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
Corresponding to the lithium ion button cell prepared in example 4And (3) performing a test, and displaying the result: at 100mAg-1The discharge capacity and the charge capacity of the lithium-ion button cell prepared in application example 4 are 663mAhg respectively under low current density-1And 634mAhg-1It is shown that the electrode material prepared in example 4 has a high specific capacity, which is higher than that of a commercial graphite anode (372 mAhg)-1) Higher by 70%. The cycle performance test of the nano-particle cathode shows excellent cycle performance.
Application example 5
Pasting 80 wt.% of the polymer mixture nanoparticles prepared in example 6, 10 wt.% of conductive carbon black and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
The lithium ion button cell prepared in the example 5 was tested, and the results show that: at 100mAg-1The discharge and charge capacities of the lithium-ion button cell prepared in application example 5 are 522mAhg respectively at low current density-1And 522mAhg-1It is shown that the electrode material prepared in example 6 has a high specific capacity. The cycle performance test of the nano-particle cathode shows excellent cycle performance.
Application example 6
Pasting 70 wt.% of the polymer mixture nanoparticles prepared in example 2, 20 wt.% of conductive carbon black and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
The lithium ion button cell prepared in example 6 was tested, and the results show that the electrode material prepared in example 2 has high specific capacity. The cycle performance test of the nano-particle cathode shows excellent cycle performance.
Application example 7
Pasting 80 wt.% of the polymer mixture nanoparticles prepared in example 3, 10 wt.% of conductive carbon black and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
The lithium ion button cell prepared in example 7 was tested, and the results show that the electrode material prepared in example 3 has high specific capacity. The cycle performance test of the nano-particle cathode shows excellent cycle performance.
Application example 8
Pasting 70 wt.% of the polymer mixture nanoparticles prepared in example 5, 20 wt.% of conductive carbon black and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
The lithium ion button cell prepared in example 8 was tested, and the results show that the electrode material prepared in example 5 has high specific capacity. The cycle performance test of the nano-particle cathode shows excellent cycle performance.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A polymer mixture for an organic electrode material, wherein the polymer comprises structural units according to formula (I):
Figure FDA0002150558060000011
wherein,
Figure FDA0002150558060000015
represents a connecting bond to an adjacent structural unit;
Figure FDA0002150558060000012
express and instituteA residue of a conjugated polycyclic aromatic compound linked by the linking bond; m is an integer of 2 or more.
2. The polymer mixture for organic electrode material according to claim 1, wherein the polymer further comprises a terminal structural unit represented by formula (II):
Figure FDA0002150558060000013
wherein, Y is each independently O or S; m1+ m2 ═ m, and m1 and m2 are integers.
3. The polymer mixture for organic electrode material according to claim 1 or 2, wherein the conjugated polycyclic aromatic compound residue is one of the following structures:
Figure FDA0002150558060000014
Figure FDA0002150558060000021
wherein R is1、R4、R5Each independently selected from alkyl, alkyl containing hetero atom or aryl with substituent;
R2、R3each independently selected from N, O, S or C, and R2And R3Connected to form a five-membered ring or a six-membered ring;
X1each independently N, P, B or CH;
X2each independently is N or CH.
4. A method for preparing a polymer mixture for an organic electrode material, comprising the steps of:
mixing a conjugated polycyclic aromatic compound containing more than two carbonyl groups with an oxygen-sulfur exchange reagent, heating and refluxing in a high-boiling point solvent for reaction, and separating and purifying after the reaction is finished to obtain a polymer mixture for the organic electrode material, wherein the polymer comprises a structural unit shown as a formula (I):
Figure FDA0002150558060000031
wherein,
Figure FDA0002150558060000034
represents a connecting bond to an adjacent structural unit;
Figure FDA0002150558060000032
represents a residue of a conjugated polycyclic aromatic compound attached to the linkage; m is an integer of 2 or more.
5. The method of claim 4, wherein the polymer further comprises a terminal structural unit represented by formula (II):
Figure FDA0002150558060000033
wherein, Y is each independently O or S; m1+ m2 ═ m, and m1 and m2 are integers.
6. The method for preparing a polymer mixture for an organic electrode material according to claim 4, wherein the conjugated polycyclic aromatic compound having two or more carbonyl groups is selected from one of the following compounds:
wherein R is1、R4、R5Each independently selected from alkyl, alkyl containing hetero atom or aryl with substituent;
R2、R3each independently selected from N, O, S or C, and R2And R3Connected to form a five-membered ring or a six-membered ring;
X1each independently N, P, B or CH;
X2each independently is N or CH.
7. The method of claim 4, wherein the oxygen-sulfur exchange reagent is selected from one or more of Lawson's reagent, Davy reagent, Japan reagent, Belleau's reagent, tetraphosphorus decasulfide, a mixture of hydrogen sulfide and hydrogen chloride, and other polysulfide-containing compounds.
8. The method for preparing a polymer mixture for an organic electrode material according to claim 4, wherein the high-boiling solvent is a solvent having a boiling point of 160 ℃ or higher.
9. The method of claim 8, wherein the high boiling point solvent is selected from one or more of trichlorobenzene, trimethylbenzene, dimethylsulfoxide, N-methylpyrrolidone, N-dimethylformamide, dimethylacetamide, N-dimethylpropylurea, 1, 3-dimethyl-2-imidazolidinone, quinoline, and diphenyl ether.
10. Use of the polymer mixture for organic electrode material according to any one of claims 1 to 3 or the polymer mixture for organic electrode material prepared by the preparation method according to any one of claims 4 to 9 in an alkali metal battery or a supercapacitor.
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