CN114006126B - Lithium-sulfur battery diaphragm material and preparation method thereof - Google Patents

Lithium-sulfur battery diaphragm material and preparation method thereof Download PDF

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CN114006126B
CN114006126B CN202111291397.0A CN202111291397A CN114006126B CN 114006126 B CN114006126 B CN 114006126B CN 202111291397 A CN202111291397 A CN 202111291397A CN 114006126 B CN114006126 B CN 114006126B
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diaphragm
polyaryletherketone
lithium
monomer
sulfur battery
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CN114006126A (en
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呼微
朱可为
刘佰军
朱广山
徐义全
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Northeast 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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 provides a lithium sulfur battery diaphragm material and a preparation method thereof, wherein polyaryletherketone and nanocellulose are compounded to prepare a diaphragm for a lithium sulfur battery by a phase inversion method, and the polyaryletherketone is prepared by bisphenol monomers and difluoro monomers; the nano cellulose is prepared by hydrolyzing micron-sized cellulose with inorganic acid. Compared with a commercial polyolefin diaphragm, the thermal stability of the diaphragm material is improved, and the diaphragm shrinkage rate is only 3.3%; meanwhile, the mechanical property, the prepared battery performance and the service life are good, the actual battery requirement can be met, and the initial discharge capacity of the prepared battery is up to 1224mAh g ‑1 The capacity retention rate of 100 circles is 24% higher than that of the polyolefin membrane over 34%. Compared with a common commercial diaphragm, the lithium-sulfur battery diaphragm is more beneficial to improving the ion conductivity and accelerating the conduction of lithium ions; the lithium sulfur battery prepared by the method has high efficiency, more stable battery performance and good commercial popularization prospect.

Description

Lithium-sulfur battery diaphragm material and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a lithium-sulfur battery diaphragm material and a preparation method thereof.
Background
Among various battery systems, lithium Ion Batteries (LIBs) have been on the battery market in portable electronic devices for over 20 years, and are currently the best choice for electric vehicles. However, as the performance of lithium ion batteries approaches its theoretical limit, their electrochemical performance is difficult to continue to improve. Meanwhile, the relatively high cost and safety of the lithium ion battery also prevent the lithium ion battery from being applied to the electric automobile in a large scale. Research and development of next-generation batteries having higher energy density and lower cost are urgently required. Lithium sulfur (Li-S) battery systems are considered as one of the promising candidates, with extremely high theoretical capacity and energy density, and at the same time, as the most promising class of existing energy storage systems. However, some disadvantages of lithium sulfur batteries, such as the shuttle effect, limit their practical use. While research into separators may provide a significant help to improve the performance of lithium sulfur batteries. In a battery system, the separator influences various factors such as internal resistance, discharge capacity, cycle performance, safety and the like of the battery. Good battery separators have requirements for their electrical insulation, porosity, corrosion resistance, wettability, mechanical properties and chemical stability. However, the current commercial separator (mostly polyethylene PE and polypropylene PP) is widely used in lithium ion batteries, but is hardly used in lithium sulfur batteries because of the inability to resist the shuttle effect of lithium sulfur batteries. Meanwhile, the porosity of the commercial diaphragm is poor in electrolyte liquid absorption, so that the battery capacity is low, and the coulombic efficiency is poor; the melting point is lower, the thermal stability is poor, and the battery has potential safety hazard in operation. Therefore, developing a special diaphragm for a lithium-sulfur battery has great significance for exerting the performance of the lithium-sulfur battery and accelerating the practical application of the lithium-sulfur battery.
Polyaryletherketone (PAEK) polymers are one of the most important members of the Polyetherketone (PEK) family, having excellent mechanical properties, chemical stability, thermal properties. And the polar group contained therein can significantly enhance the electrolyte absorbing ability of the separator. The Sulfonated Polyaryletherketone (SPAEK) is prepared by sulfonating PAEK polymer or polymerizing monomer containing sulfonate group through polymerization reaction. The mechanical properties and the thermal properties of the polyaryletherketone can be kept to a certain extent after sulfonation, and the sulfonate groups introduced by sulfonation can repel polysulfide ions by the principle of anion electrostatic repulsion to inhibit the shuttle effect, but the mechanical properties of the polyaryletherketone are inevitably influenced by the sulfonation, so that the technical problem to be solved is that how to reduce the reduction of the mechanical properties of the polyaryletherketone and apply the polyaryletherketone to a lithium-sulfur battery diaphragm.
Cellulose is one of the most abundant macromolecules in nature, and has the characteristics of reproducibility, biodegradability, good hydrophilicity and the like. The main structural unit being a glucosyl group, adjacent groups being linked by glycosidic bonds, the formula being (C 6 H 10 O 5 ) n, nanocellulose (Nanocrystalline Cellulose, NCC) is a rod-shaped nanoparticle, nanocellulose with a length between 100 and 2000nm and a diameter between 2 and 100 nm. Because nanocellulose has the above-mentioned superior properties, it can be used as a potential filler for high-strength, biocompatible and biodegradable films. How to compound the NCC with the sulfonated polyaryletherketone to be used for improving the mechanical property, inhibiting the shuttle effect and improving the performance of the lithium-sulfur battery diaphragm is also a technical problem to be solved urgently at present. The existing lithium sulfur battery diaphragm has the problems of high cost and high energy consumption. Patent document CN108511664a discloses a lithium sulfur battery separator, which is prepared by calcining PEG and titanium dioxide at 900 ℃ to prepare a titanium dioxide porous material. The energy consumption is too large, and the industrial production is not facilitated. Patent document CN112864527a discloses a lithium-sulfur battery modified separator, which mixes Mxene material with ferric nitrate nonahydrate, dopamine and amino acid, and heats for 2-3 hours at 200-300 ℃ in a tube furnace under nitrogen atmosphere. Expensive materials are used, the reaction steps are complex, and various organic solvents are used in the reaction, so that the method is not beneficial to environment friendliness.
In summary, although various lithium sulfur battery separators are disclosed in the prior art, there is a great room for improvement in cost control, productivity and environmental friendliness. In view of the actual production requirements, there is a need to develop a lithium sulfur battery separator that can meet both the use and production requirements.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lithium-sulfur battery diaphragm material, and the preparation method comprises the following steps: mixing sulfuric acid solution and methane sulfonic acid according to a mass ratio of 1:15-1:5 to obtain a mixed acid solution, and adding nano-particles into the mixed acid solutionCellulose and polyaryletherketone, according to the mass ratio: stirring for 24-144 hr to obtain film coating solution with nanometer cellulose 0.5-2% and polyaryletherketone 6-10%, spreading polyolefin film on glass plate, sucking film coating solution to drop on the polyolefin film, and stirring according to 0.5-2 cm.s -1 The method comprises the steps of (1) scraping a film to obtain a coated polyolefin wet film, taking a solvent as a coagulating bath, placing the coated polyolefin wet film in the coagulating bath, carrying out phase inversion at room temperature to obtain phase inversion polyaryletherketone and a nanocellulose coated polyolefin diaphragm, taking out the coated polyolefin diaphragm, placing the coated polyolefin diaphragm in pure water for soaking to remove a salt solution, and drying at the temperature of 60-90 ℃ in vacuum to obtain a lithium-sulfur battery diaphragm material; wherein the structural formula of the polyaryletherketone is as follows:
Figure GDA0003384226320000021
，
wherein X, Y and Z are positive integers, X is more than or equal to 6 and less than or equal to 63; y is more than or equal to 46 and less than or equal to 63; z is more than or equal to 46 and less than or equal to 63; wherein R is 1 -R 7 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy, and the polyolefin is any combination of polyethylene and polypropylene; the coagulating bath is one of water or a mixed solution of ethanol and water, a mixed solution of acetone and water or a mixed solution of n-butanol and water; the concentration of the sulfuric acid is 90-98%; the concentration of the methane sulfonic acid is 95-99%.
Further, the nanocellulose is prepared by the following method: adding acid into micron-sized cellulose, stirring at 30-70 ℃ for 1-8 hours to obtain a cellulose solution, pouring the cellulose solution into deionized water to obtain a mixed solution, standing the mixed solution for 10-48 hours, removing supernatant, adding deionized water to obtain a suspension, centrifuging the suspension for 10-40 minutes to remove supernatant, and rotating at the speed: 500-1500rpm, repeatedly adding deionized water and centrifuging for 2-8 times to obtain cellulose suspension, placing the suspension into a dialysis bag, dialyzing to remove acid, and freeze-drying to obtain nanocellulose, wherein the acid is sulfuric acid or hydrochloric acid or nitric acid, the mass fraction of sulfuric acid is 40-80%, the mass fraction of hydrochloric acid is 10-30%, and the mass fraction of nitric acid is 30-60%.
Further, the polyaryletherketone is prepared by the following method: according to the mol ratio of 1:1-10:1-10 mixing a monomer 1, a monomer 2 and a monomer 3, adding a monomer 4 with the mass 1-1.2 times of the total sum of the monomer 1, the monomer 2 and the monomer 3, adding an organic solvent, a Lewis base and a catalyst, and heating at 220 ℃ for 5 hours to react to obtain the polyaryletherketone, wherein the structure of the monomer 1 is as follows:
Figure GDA0003384226320000031
wherein R is 1 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy;
R 2 is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy;
the structure of the monomer 2 is as follows:
Figure GDA0003384226320000032
wherein R is 3 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy;
R 4 is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy; r is R 5 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy;
the structure of the monomer 3 is as follows:
Figure GDA0003384226320000041
wherein R is 6 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy;
R 7 is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy;
the monomer 4 is 1, 4-bis (4-fluorobenzoyl) benzene, and the structure is that
Figure GDA0003384226320000042
The organic solvent is one of benzene, toluene, dimethylformamide, dimethyl sulfoxide, n-hexane or heptane; the Lewis base is selected from one of diphenyl sulfone, sulfolane or N-methyl pyrrolidone; the catalyst is sodium carbonate or potassium carbonate.
The invention provides a polyaryletherketone polymer/nanocellulose composite material with a specific structure, which is used as a coating of a polyolefin diaphragm, so that the diaphragm can resist lithium sulfur shuttle effect and simultaneously can maintain good thermal performance, mechanical performance and electrochemical performance.
The invention adopts polyaryletherketone with a specific structure as a heat-resistant material of the lithium-sulfur battery diaphragm, and the most preferred proportion of the polyaryletherketone and the matrix diaphragm is obtained by screening, so that the prepared lithium-sulfur battery diaphragm has excellent comprehensive performance, can completely meet the requirements of actual production and application, has a simple preparation method, is easy to obtain raw materials, and has great commercial application potential.
Compared with the prior art, the lithium sulfur battery diaphragm prepared by taking the polyaryletherketone with the specific structure as the heat-resistant material has the following beneficial effects:
1. the polyaryletherketone with a specific structure is prepared by selecting specific monomer types, and the mechanical property and the heat resistance of the diaphragm material can be effectively improved on the premise of resisting the shuttle effect of the lithium-sulfur battery.
2. When the lithium-sulfur battery diaphragm is prepared, the concentration of polyaryletherketone, the preparation method of nanocellulose and the conditions of a coagulating bath are also screened, so that the optimal film forming processing conditions are obtained. The lithium sulfur battery diaphragm prepared under the condition has excellent discharge capacity and coulombic efficiency, has a good pore diameter distribution detour structure, is favorable for conducting lithium ions and improving the battery performance, and further improves the battery performance and service life.
Drawings
FIG. 1 is a bar graph of tensile strength of the separator of comparative example 2, the separator of examples 6,7,8, 9;
fig. 2 (a) is an SEM photograph of the comparative example 2 separator (PAEK, 6.5%); fig. 2 (b) is an SEM photograph of the separator of example 6 (PAEK, 6.5%, NCC, 0.5%); fig. 2 (c) SEM photograph of the separator of example 7 (PAEK, 6.5%, NCC, 1.5%);
FIG. 3 is a graph of the cell performance of the comparative example 2 separator and the example 6,7,8 separators;
FIG. 4 is a graph showing the performance curves of the comparative example 2 and example 6,7,8 separators at different currents.
Detailed Description
The present invention will be described in further detail with reference to specific examples, for the purpose of making the present application more clearly understood and appreciated by those skilled in the art. The following specific examples are not to be construed or interpreted in any way as limiting the scope of the claims. For example, the values of points or specific substances disclosed in the examples should not be limited to the values of points or specific substances, but other numerical ranges or substances that can reasonably be expected by a person skilled in the art to exert the same function.
Unless otherwise specified, the reagents employed in the present invention are all conventional commercially available reagents.
Example 1
(1)Preparation of nanocellulose 1
The method comprises the following specific steps: 250mL of sulfuric acid (64% by mass fraction) was added to 15g of commercial micron-sized cellulose (cas: 9004-34-6, purchased from Allatin), a cellulose solution was obtained after stirring at 45℃for 3 hours, the cellulose solution was poured into 2.5L of deionized water to obtain a mixed solution, the mixed solution was allowed to stand for 12 hours, the supernatant was removed, deionized water was added to obtain a suspension, the suspension was centrifuged (rotation speed: 1000 rpm) for 10 minutes to remove the supernatant, deionized water and centrifugation were repeated for 3-5 times to obtain a cellulose suspension, the suspension was placed in a dialysis bag, the acid was removed by dialysis, and the nanocellulose 1 (NCC 1) was obtained after lyophilization.
(2)Preparation of nanocellulose 2
The method comprises the following specific steps: 250mL of sulfuric acid (74% by mass fraction) was added to 15g of commercial micron-sized cellulose (cas: 9004-34-6, purchased from Allatin), a cellulose solution was obtained after stirring at 55℃for 4 hours, the cellulose solution was poured into 2.5L of deionized water to obtain a mixed solution, the mixed solution was allowed to stand for 24 hours, the supernatant was removed, deionized water was added to obtain a suspension, the suspension was centrifuged (rotation speed: 1000 rpm) for 10 minutes to remove the supernatant, deionized water and centrifugation were repeated for 3-5 times to obtain a cellulose suspension, the suspension was placed in a dialysis bag, the acid was removed by dialysis, and the nanocellulose 2 (NCC 2) was obtained after lyophilization.
(3)Preparation of nanocellulose 3
The method comprises the following specific steps: 250mL of sulfuric acid (54% by mass fraction) was added to 15g of commercial micron-sized cellulose (cas: 9004-34-6, purchased from Allatin), a cellulose solution was obtained after stirring at 65℃for 5 hours, the cellulose solution was poured into 2.5L of deionized water to obtain a mixed solution, the mixed solution was allowed to stand for 48 hours, the supernatant was removed, deionized water was added to obtain a suspension, the suspension was centrifuged (rotation speed: 1000 rpm) for 10 minutes to remove the supernatant, deionized water and centrifugation were repeated for 3-5 times to obtain a cellulose suspension, the suspension was placed in a dialysis bag, the acid was removed by dialysis, and the nanocellulose 3 (NCC 3) was obtained after lyophilization.
(4)Preparation of polyaryletherketone 1
In a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet pipe, a thermometer and a water separator, o-diphenylbenzenediol (0.1 mol), 3-bis (4-hydroxyphenyl) phenylpropionic acid (0.1 mol), 2, 4-bis (2-hydroxy-5-biphenyl) propylene (0.1 mol), 1, 4-bis (4-fluorobenzoyl) benzene (0.3 mol), anhydrous potassium carbonate (0.63 mol), sulfolane (TMS) 72mL and toluene 35mL were sequentially added, nitrogen was introduced, the temperature was raised to 140 ℃ under stirring to react for 3 hours, the water generated by the reaction was thoroughly carried out, and then the temperature was raised to give a thick toluene, and the toluene was further raised to 220 ℃ to react for 5 hours to obtain a viscous solution. Adding the viscous solution into distilled water, cooling, pulverizing, washing with deionized water and ethanol for 5 times, and vacuum drying at 100deg.C for 24 hr. The product polyaryletherketone 1 (PAEK 1) was obtained.
Figure GDA0003384226320000061
Wherein X is 43; y is 43; z is 43.
(5)Preparation of polyaryletherketone 2
In a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet pipe, a thermometer and a water separator, o-diphenylbenzenediol (0.1 mol), 3-bis (4-hydroxyphenyl) phenylpropionic acid (0.2 mol), 2, 4-bis (2-hydroxy-5-biphenyl) propylene (0.2 mol), 1, 4-bis (4-fluorobenzoyl) benzene (0.5 mol), anhydrous potassium carbonate (0.63 mol), sulfolane (TMS) 72ml and toluene 35m L were sequentially added, nitrogen was introduced, the temperature was raised to 140 ℃ with stirring to react for 3 hours, after the water generated by the reaction was thoroughly carried out, toluene was continuously heated to give a thick solution, and the thick solution was then heated to 220 ℃ to react for 5 hours. Adding the viscous solution into distilled water, cooling, pulverizing, washing with deionized water and ethanol for 5 times, and vacuum drying at 100deg.C for 24 hr. The product polyaryletherketone 2 (PAEK 2) was obtained.
Figure GDA0003384226320000071
Wherein X is 23; y is 46; z is 46.
(6)Preparation of polyaryletherketone 3
In a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet pipe, a thermometer and a water separator, o-diphenylbenzenediol (0.1 mol), 3-bis (4-hydroxyphenyl) phenylpropionic acid (0.3 mol), 2, 4-bis (2-hydroxy-5-biphenyl) propylene (0.3 mol), 1, 4-bis (4-fluorobenzoyl) benzene (0.7 mol), anhydrous potassium carbonate (0.63 mol), sulfolane (TMS) 72mL and toluene 35mL were sequentially added, nitrogen was introduced, the temperature was raised to 140 ℃ under stirring to react for 3 hours, the water generated by the reaction was thoroughly carried out, then the temperature was raised to give a thick toluene, and the toluene was further raised to 220 ℃ to react for 5 hours to obtain a viscous solution. Adding the viscous solution into distilled water, cooling, pulverizing, washing with deionized water and ethanol for 5 times, and vacuum drying at 100deg.C for 24 hr. The product polyaryletherketone 3 (PAEK 3) was obtained.
Figure GDA0003384226320000072
Wherein X is 17; y is 51; z is 51.
(7)Preparation of polyaryletherketone 4
In a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet pipe, a thermometer and a water separator, o-diphenylbenzenediol (0.1 mol), 3-bis (4-hydroxyphenyl) phenylpropionic acid (0.4 mol), 2, 4-bis (2-hydroxy-5-biphenyl) propylene (0.4 mol), 1, 4-bis (4-fluorobenzoyl) benzene (0.9 mol), anhydrous potassium carbonate (0.63 mol), sulfolane (TMS) 72mL and toluene 35mL were sequentially added, nitrogen was introduced, the temperature was raised to 140 ℃ under stirring to react for 3 hours, the water generated by the reaction was thoroughly carried out, then the temperature was raised to give a thick toluene, and the toluene was further raised to 220 ℃ to react for 5 hours to obtain a viscous solution. Adding the viscous solution into distilled water, cooling, pulverizing, washing with deionized water and ethanol for 5 times, and vacuum drying at 100deg.C for 24 hr. The product polyaryletherketone 4 (PAEK 4) was obtained.
Figure GDA0003384226320000081
Wherein X is 13; y is 52; z is 52.
(8)Preparation of polyaryletherketone 5
In a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet pipe, a thermometer and a water separator, o-diphenylbenzenediol (0.1 mol), 3-bis (4-hydroxyphenyl) phenylpropionic acid (0.5 mol), 2, 4-bis (2-hydroxy-5-biphenyl) propylene (0.5 mol), 1, 4-bis (4-fluorobenzoyl) benzene (1.1 mol), anhydrous potassium carbonate (0.63 mol), sulfolane (TMS) 72mL and toluene 35mL were sequentially added, nitrogen was introduced, the temperature was raised to 140 ℃ under stirring to react for 3 hours, the water generated by the reaction was thoroughly carried out, and then the temperature was raised to give a thick toluene, and the toluene was further raised to 220 ℃ to react for 5 hours to obtain a viscous solution. Adding the viscous solution into distilled water, cooling, pulverizing, washing with deionized water and ethanol for 5 times, and vacuum drying at 100deg.C for 24 hr. The product polyaryletherketone 5 (PAEK 5) was obtained.
Figure GDA0003384226320000082
Wherein X is 10; y is 50; z is 50.
(9)Preparation of polyaryletherketone 6
In a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet pipe, a thermometer and a water separator, o-diphenylbenzenediol (0.1 mol), 3-bis (4-hydroxyphenyl) phenylpropionic acid (0.6 mol), 2, 4-bis (2-hydroxy-5-biphenyl) propylene (0.6 mol), 1, 4-bis (4-fluorobenzoyl) benzene (1.3 mol), anhydrous potassium carbonate (0.63 mol), sulfolane (TMS) 72mL and toluene 35mL were sequentially added, nitrogen was introduced, the temperature was raised to 140 ℃ under stirring to react for 3 hours, the water generated by the reaction was thoroughly carried out, and then the temperature was raised to give a thick toluene, and the toluene was further raised to 220 ℃ to react for 5 hours to obtain a viscous solution. Adding the viscous solution into distilled water, cooling, pulverizing, washing with deionized water and ethanol for 5 times, and vacuum drying at 100deg.C for 24 hr. The product polyaryletherketone 6 (PAEK 6) was obtained.
Figure GDA0003384226320000091
Wherein X is 9; y is 54; z is 54.
(10)Preparation of polyaryletherketone 7
In a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet pipe, a thermometer and a water separator, o-diphenylbenzenediol (0.1 mol), 3-bis (4-hydroxyphenyl) phenylpropionic acid (0.7 mol), 2, 4-bis (2-hydroxy-5-biphenyl) propylene (0.7 mol), 1, 4-bis (4-fluorobenzoyl) benzene (1.5 mol), anhydrous potassium carbonate (0.63 mol), sulfolane (TMS) 72mL and toluene 35mL were sequentially added, nitrogen was introduced, the temperature was raised to 140 ℃ under stirring to react for 3 hours, the water generated by the reaction was thoroughly carried out, and then the temperature was raised to give a thick toluene, and the toluene was further raised to 220 ℃ to react for 5 hours to obtain a viscous solution. Adding the viscous solution into distilled water, cooling, pulverizing, washing with deionized water and ethanol for 5 times, and vacuum drying at 100deg.C for 24 hr. The product polyaryletherketone 7 (PAEK 7) was obtained.
Figure GDA0003384226320000101
Wherein X is 7; y is 49; z is 49.
(11)Preparation of polyaryletherketone 8
In a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet pipe, a thermometer and a water separator, o-diphenylbenzenediol (0.1 mol), 3-bis (4-hydroxyphenyl) phenylpropionic acid (0.8 mol), 2, 4-bis (2-hydroxy-5-biphenyl) propylene (0.8 mol), 1, 4-bis (4-fluorobenzoyl) benzene (1.7 mol), anhydrous potassium carbonate (0.63 mol), sulfolane (TMS) 72mL and toluene 35mL were sequentially added, nitrogen was introduced, the temperature was raised to 140 ℃ under stirring to react for 3 hours, the water generated by the reaction was thoroughly carried out, and then the temperature was raised to give a thick toluene, and the toluene was further raised to 220 ℃ to react for 5 hours to obtain a viscous solution. Adding the viscous solution into distilled water, cooling, pulverizing, washing with deionized water and ethanol for 5 times, and vacuum drying at 100deg.C for 24 hr. The product polyaryletherketone 8 (PAEK 8) was obtained.
Figure GDA0003384226320000102
Wherein X is 6; y is 48; z is 48.
(12)Preparation of polyaryletherketone 9
In a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet pipe, a thermometer and a water separator, o-diphenylbenzenediol (0.1 mol), 3-bis (4-hydroxyphenyl) phenylpropionic acid (0.9 mol), 2, 4-bis (2-hydroxy-5-biphenyl) propylene (0.9 mol), 1, 4-bis (4-fluorobenzoyl) benzene (1.9 mol), anhydrous potassium carbonate (0.63 mol), sulfolane (TMS) 72mL and toluene 35mL were sequentially added, nitrogen was introduced, the temperature was raised to 140 ℃ under stirring to react for 3 hours, the water generated by the reaction was thoroughly carried out, and then the temperature was raised to give a thick toluene, and the toluene was further raised to 220 ℃ to react for 5 hours to obtain a viscous solution. Adding the viscous solution into distilled water, cooling, pulverizing, washing with deionized water and ethanol for 5 times, and vacuum drying at 100deg.C for 24 hr. The product polyaryletherketone 9 (PAEK 9) was obtained.
Figure GDA0003384226320000111
Wherein X is 6; y is 54; z is 54.
The product polyaryletherketone prepared by the method is characterized, and the weight average molecular weight, the glass transition temperature and the mechanical property of the product polyaryletherketone are tested. The results are shown in table 1 below:
the weight average molecular weight was measured by static light scattering, and the instrument was Autosizer 4700 from Markov, UK.
The glass transition temperature (Tg) is obtained by DSC thermal analysis, the instrument is an automatic differential scanning calorimeter in Shimadzu DSC-60 type, the test condition is that the temperature rising rate is 10K/min, N 2 An atmosphere.
Tensile strength test: the drawing speed is 10mm/min by being carried out on a domestic KT877S type electronic universal tester.
TABLE 1 weight average molecular weight, glass transition temperature and mechanical Property of polyaryletherketone 1-9
Figure GDA0003384226320000112
As can be seen from the data in Table 1, the polyaryletherketone prepared by the invention has excellent comprehensive performance, shows good heat-resistant stability, can keep lower glass transition temperature, and is convenient for post-processing; meanwhile, the mechanical property is good, and the tensile strength is more than 86-108 Mpa.
Example 2Preparation of lithium sulfur battery separator 1
2ml of sulfuric acid solution and 25ml of methanesulfonic acid are mixed to obtain a mixed acid solution, 0.026g of nanofiber 1 (NCC 1) is added, after full stirring for 24 hours, 2.6g of polyaryletherketone 1 (PAEK 1) is added, and full stirring is carried out for 24 hours, so as to obtain a film coating solution, wherein the mass concentration of PAEK1 is 6.5%, and the mass concentration of NCC is 0.5%. Cutting a Polyethylene (PE) diaphragm into a film of 6 x 14cm, placing the PE film on a glass plate, and paving; 2mL of the coating solution was pipetted onto the PE film according to 0.5 cm.s -1 The film was scraped to obtain a coated PE wet film. The pure water is taken as a coagulating bath, the coated PE wet film is placed in the coagulating bath, and phase inversion is carried out at 25 ℃ to obtain the PAEK1/NCC1 coated PE diaphragm with phase inversion. Taking out the PE membrane, soaking in pure water to remove salt solution, and vacuum drying at 70deg.C to obtainLithium sulfur battery separator 1.
Examples 3 to 9Preparation of lithium sulfur battery separator 2-8
Examples 3-9 lithium sulfur battery separators were prepared according to the same raw material polyaryletherketone 1 (PAEK 1), nanocellulose (NCC 1) and method as in example 2, except that the addition amounts of polyaryletherketone 1 (PAEK 1), nanocellulose (NCC 1) were different, and coagulation bath conditions were changed, and the reaction raw material concentrations and coagulation bath conditions of examples 3-9 are shown in table 2, respectively, to obtain lithium sulfur battery separators 2, 3, 4, 5, 6,7 and 8.
Example 10 a mixed acid solution is obtained by mixing 2ml of sulfuric acid solution with 20ml of methanesulfonic acid, 0.052g of nanofiber 1 (NCC 1) is added, after full stirring for 24 hours, 2.6g of polyaryletherketone 2 (PAEK 2) is added, and full stirring is carried out for 24 hours, a film coating solution is obtained, wherein the mass concentration of PAEK2 is 8%, a Polyethylene (PE) diaphragm is cut into a film of 6 x 14cm, and the PE film is placed on a glass plate and is paved; sucking 2mL of the film coating solution to drop on the PE film according to the thickness of 1 cm.s -1 The film was scraped to obtain a coated PE wet film. Mixing pure water and ethanol to obtain a coagulating bath, placing the coated PE wet film in the coagulating bath, and carrying out phase inversion at 25 ℃ to obtain the phase-inverted PAEK2/NCC1 coated PE diaphragm. And taking out the PE-coated diaphragm, soaking in pure water to remove salt solution, and drying at the temperature of 70 ℃ in vacuum to obtain the lithium-sulfur battery diaphragm 10.
Example 11 a mixed acid solution is obtained by mixing 2ml of sulfuric acid solution with 30ml of methanesulfonic acid, 0.034g of nanofiber 1 (NCC 2) is added, after full stirring for 24 hours, 2.6g of polyaryletherketone 3 (PAEK 3) is added, full stirring is carried out for 48 hours, a film coating solution is obtained, wherein the mass concentration of PAEK3 is 7%, a Polyethylene (PE) diaphragm is cut into a film of 6 x 14cm, and the PE film is placed on a glass plate and is paved; 2mL of the coating solution was pipetted onto the PE film according to 1.5 cm.s -1 The film was scraped to obtain a coated PE wet film. Mixing pure water and ethanol to obtain a coagulating bath, placing the coated PE wet film in the coagulating bath, and carrying out phase inversion at 25 ℃ to obtain the phase-inverted PAEK3/NCC2 coated PE diaphragm. And taking out the PE-coated diaphragm, soaking in pure water to remove salt solution, and drying at the temperature of 70 ℃ in vacuum to obtain the lithium-sulfur battery diaphragm 11.
EXAMPLE 122 ml sulfuric acidMixing the solution with 35ml of methane sulfonic acid to obtain a mixed acid solution, adding 0.046g of nanofiber 1 (NCC 3), fully stirring for 24 hours, adding 3.8g of polyaryletherketone 4 (PAEK 4), fully stirring for 72 hours to obtain a film coating solution, wherein the mass concentration of the PAEK4 is 9%, cutting a Polyethylene (PE) diaphragm into a film of 6 x 14cm, placing the PE film on a glass plate, and paving; sucking 2mL of the film coating solution to drop on the PE film according to the thickness of 2 cm.s -1 The film was scraped to obtain a coated PE wet film. Mixing pure water and ethanol to obtain a coagulating bath, placing the coated PE wet film in the coagulating bath, and carrying out phase inversion at 25 ℃ to obtain the phase-inverted PAEK4/NCC3 coated PE diaphragm. And taking out the PE-coated diaphragm, soaking in pure water to remove salt solution, and drying at the temperature of 70 ℃ in vacuum to obtain the lithium-sulfur battery diaphragm 12.
TABLE 2 concentration of the reaction raw materials and coagulation bath conditions for examples 2 to 9
Figure GDA0003384226320000131
Comparative example 1
Commercial PE diaphragms are directly adopted.
Comparative example 2
Mixing 2ml of sulfuric acid solution with 25ml of methanesulfonic acid to obtain a mixed acid solution, adding 2.6g of polyaryletherketone 1 (PAEK 1), and fully stirring for 24 hours to obtain a film coating solution, wherein the mass concentration of the PAEK1 is 6.5%, cutting a Polyethylene (PE) diaphragm into a film with the mass concentration of 6 x 14cm, placing the PE film on a glass plate, and paving; 2mL of the coating solution was pipetted onto the PE film according to 0.5 cm.s -1 The film was scraped to obtain a coated PE wet film. And taking pure water as a coagulating bath, placing the coated PE wet film in the coagulating bath, carrying out phase inversion at 25 ℃ to obtain a PAEK1 coated PE diaphragm with phase inversion, taking out the coated PE diaphragm, placing the coated PE diaphragm in pure water, soaking to remove salt solution, and carrying out vacuum drying to obtain the lithium-sulfur battery diaphragm.
Performance testing
The lithium sulfur battery separators of examples 2 to 9 and comparative examples 1 and 2 were subjected to the following performance tests:
(1) The lithium sulfur battery separator was tested for thermal stability and the results are shown in table 3 below:
table 3 thermal stability testing of lithium sulfur battery separators of the composites of examples 2-9 and comparative examples 1, 2
Figure GDA0003384226320000141
T 5 And T 10 The meaning of (2) is that the temperature of the thermal weight loss of 5% of the mass loss of the diaphragm and the temperature of the thermal weight loss of 10% of the mass loss of the diaphragm are tested by a thermal weight loss analyzer under the temperature rising rate of 25-700 ℃ and 10 ℃/min. Wherein the heat shrinkage means after 30 minutes of treatment at 180 ℃.
As can be seen from Table 3, compared with comparative example 1, the thermal stability of the PAEK and NCC coated PE lithium sulfur battery separator prepared by the embodiment of the invention is improved, T 5 Up to 343.8 ℃, T 10 Up to 483.9 ℃. After 0.5h of treatment at 180 ℃, comparative example 1 almost disappeared and the shrinkage reached 100%, PAEK coated PE lithium sulfur battery separator in examples 2, 5, 6 showed excellent heat shrinkage resistance. The heat shrinkage of the PAEK coated PE lithium sulfur battery separator in the preferred embodiment 6 of the invention is only 3.3%.
(2) The mechanical properties of the lithium sulfur battery separator were tested, and the results are shown in the following table 4:
the tensile strength was measured on a domestic KT877S electronic universal tester at a tensile rate of 10mm/min.
Test of elongation at break: the drawing speed is 10mm/min by being carried out on a domestic KT877S type electronic universal tester.
Young's modulus was measured according to ASTM C769-2009 standard.
Table 4 mechanical property test of lithium sulfur battery separator of composite materials of examples 2 to 9 and comparative example 2
Figure GDA0003384226320000151
As can be seen from Table 4 and the accompanying FIG. 1 of the specification, example 6 gives the highest mechanical properties. And the PAEK/NCC mixed solution concentration and the treatment mode of the coagulating bath are different in the preparation process, so that the mechanical properties of the diaphragm are influenced. The greater the PAEK and NCC concentrations, the more the mechanical properties decrease; in addition, the mechanical properties of the resulting membrane are affected by the way of the coagulation bath with ethanol/water.
(3) SEM photographs of lithium sulfur battery separator;
fig. 2 (a) of the drawing is an SEM image of the lithium sulfur battery separator of comparative example 2, (b) of example 6, and (c) of example 7, and it can be seen that the lithium sulfur battery separator obtained in examples 6 to 7 using ethanol and water as coagulation baths has a large pore diameter, is uniformly distributed, and generates intricate small pores inside the large pores. And compared with comparative example 2, the inside of the pores of examples 6 and 7 is enriched with carbon nanoparticles converted from NCC, which is beneficial to the inhibition of shuttle effect and the conduction of lithium ions while improving the capacity and the coulombic efficiency.
(4) And testing the battery performance of the lithium sulfur battery diaphragm.
The porous diaphragm prepared by the invention is assembled into a CR2025 button half-cell according to the following steps: 1) Mixing 60wt% of sublimed sulfur, 30wt% of acetylene black and 10wt% of polyvinylidene fluoride in N-methyl pyrrolidone, coating the mixture on an aluminum foil, drying and slicing the mixture to prepare an anode; 2) Cutting the lithium sulfur battery diaphragm prepared by the invention into a shape suitable for a CR2025 battery shell for standby; 3) The electrolyte adopts LiTFSI of 1M, the solvent is DME/DOL with the volume ratio of 1:1, and the cathode is lithium foil; 4) The above-described assembly was assembled into a CR2025 type battery in a glove box in a layered structure of positive electrode/separator/negative electrode. After the battery is assembled, the button cell is placed in a multi-channel battery tester (Xinwei) for testing. The results are shown in Table 5:
table 5 battery properties of separator materials obtained from the composites of comparative examples 1-2 and examples 2-9
Figure GDA0003384226320000161
The battery performance of the separators of the comparative examples and examples can be seen from table 5 and fig. 3 of the specification.Comparative example 2 Battery separator initial discharge capacitance was 972 mAh.g -1 The coulomb efficiency is 91%, and the capacity is rapidly reduced after the cycle, and only about 65% of the capacity is reserved after 100 cycles, which indicates that the inhibition capability on the shuttle effect is limited; while the initial discharge capacity of the PAEK/NCC coated PE separator in example 6 was as high as 1224 mAh.g -1 The coulombic efficiency can be maintained around 99%, which is an increase in initial capacity of 34% and 26% respectively compared to comparative examples 1 and 2, and after 100 cycles the retention capacity is 24% higher than that after 100 cycles compared to the PE membrane (comparative example 1) and 18% higher than that after 100 cycles compared to the comparative example 2 membrane. It is shown that the carbon nanoparticles converted from NCC play a role in capacity improvement, and hydroxyl groups, sulfonic acid groups and the like carried by NCC can further inhibit the shuttle effect, which is obvious in the figure 3 of the specification, but the larger the addition amount is, the better the performance of the membrane material is determined by the synergistic effect of the components and the process; in the embodiment 7, the NCC is excessively added and cannot be completely dispersed in the casting solution, so that the phenomenon of hole blocking is caused, and the performance is reduced; in examples 8 and 9, too much PAEK content resulted in too high a concentration of the casting solution, and increased film thickness during phase inversion, resulting in increased resistance, and longer ion passage path, resulting in reduced performance. This demonstrates that the cell performance is determined by the synergy of the components content, the ratio of the components and the reaction conditions of the separator material, which synergistically results in the separator material inhibiting the shuttling effect and not impeding lithium ion migration, wherein the synergy of the components and the reaction conditions in example 6 allows the material performance to reach an optimal value. It can be seen from this that the battery performance of the composite material of the present invention is achieved by the synergistic effect of the components, reaction conditions.
From the description of fig. 4, it can be seen that the separators of the comparative examples and examples have cell performance at different currents. Wherein the comparison 2 not only produces a significant decay with constant current, but also suffers considerable disturbance with varying current. Whereas example 6 provides almost no disturbance in each case and can still return to approximately 99% of the capacity when the current returns to 0.2C, this result is that stability at constant current is provided due to PAEK's shuttle effect inhibition and conductivity caused by NCC converted carbon nanoparticles is higher than that of the comparative example. Also, examples 7,8, while higher than the results of comparative example 2, were lower than the performance of example 6, thereby further demonstrating that the battery performance of the separator of the present invention is determined by the synergy of the components, content ratios, and reaction conditions.
TABLE 6 ionic conductivity of the composites of comparative examples 1-2 and example 6
Figure GDA0003384226320000171
The ionic conductivities of the comparative examples and examples can be seen from table 6. It can be seen that the ionic conductivity of comparative example 2 is significantly reduced from that of comparative example 1, presumably because the separator is thickened by the phase inversion layer, so that ion migration is hindered. Whereas the ionic conductivity of example 6 was significantly increased compared to comparative example 2 and comparative example 1, since the synergy of NCC and polyaryletherketone facilitates ion transport, resulting in improved ionic conductivity.
Table 7 comparison of various data for comparative example 1 (commercial separator) and example 6
Figure GDA0003384226320000172
From the comparison of the above data, it can be seen that: the lithium-sulfur battery diaphragm prepared from the polyaryletherketone and the nanocellulose has excellent comprehensive performance, and can realize that the current commercial diaphragm can not obviously inhibit the shuttle effect in terms of battery performance, thereby greatly slowing down capacity attenuation, obviously improving coulomb efficiency and ensuring the high capacity advantage of the lithium-sulfur battery. In the aspect of battery safety, the battery can greatly surpass a commercial diaphragm in the aspects of mechanical property and thermal stability, and the safety of battery operation is ensured. The preparation method is simple and convenient, the material cost is relatively low, an organic solvent harmful to the environment is not used, the method has good commercial popularization prospect, and a step is provided for the application of the lithium-sulfur battery.

Claims (3)

1. A lithium sulfur battery diaphragm material is characterized in that: the preparation method comprises the following steps: mixing sulfuric acid solution and methane sulfonic acid according to a mass ratio of 1:15-1:5 to obtain a mixed acid solution, adding nanocellulose and polyaryletherketone into the mixed acid solution, wherein the mass ratio is as follows: stirring for 24-144 hr to obtain film coating solution with nanometer cellulose 0.5-2% and polyaryletherketone 6-10%, spreading polyolefin film on glass plate, sucking film coating solution to drop on the polyolefin film, and stirring according to 0.5-2 cm.s -1 The method comprises the steps of (1) scraping a film to obtain a coated polyolefin wet film, taking a solvent as a coagulating bath, placing the coated polyolefin wet film in the coagulating bath, carrying out phase inversion at room temperature to obtain phase inversion polyaryletherketone and a nanocellulose coated polyolefin diaphragm, taking out the coated polyolefin diaphragm, placing the coated polyolefin diaphragm in pure water for soaking to remove a salt solution, and drying at the temperature of 60-90 ℃ in vacuum to obtain a lithium-sulfur battery diaphragm material; wherein the structural formula of the polyaryletherketone is as follows:
Figure FDA0003331467810000011
，
wherein X, Y and Z are positive integers, X is more than or equal to 6 and less than or equal to 63; y is more than or equal to 46 and less than or equal to 63; z is more than or equal to 46 and less than or equal to 63; wherein R is 1 -R 7 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy, and the polyolefin is any combination of polyethylene and polypropylene; the coagulating bath is one of water or a mixed solution of ethanol and water, a mixed solution of acetone and water or a mixed solution of n-butanol and water; the concentration of the sulfuric acid is 90-98%; the concentration of the methane sulfonic acid is 95-99%.
2. The lithium sulfur battery separator material according to claim 1, wherein: the nanocellulose is prepared by the following method: adding acid into micron-sized cellulose, stirring at 30-70 ℃ for 1-8 hours to obtain a cellulose solution, pouring the cellulose solution into deionized water to obtain a mixed solution, standing the mixed solution for 10-48 hours, removing supernatant, adding deionized water to obtain a suspension, centrifuging the suspension for 10-40 minutes to remove supernatant, and rotating at the speed: 500-1500rpm, repeatedly adding deionized water and centrifuging for 2-8 times to obtain cellulose suspension, placing the suspension into a dialysis bag, dialyzing to remove acid, and freeze-drying to obtain nanocellulose, wherein the acid is sulfuric acid or hydrochloric acid or nitric acid, the mass fraction of sulfuric acid is 40-80%, the mass fraction of hydrochloric acid is 10-30%, and the mass fraction of nitric acid is 30-60%.
3. A lithium sulfur battery separator material according to claim 1 or 2, characterized in that: the polyaryletherketone is prepared by the following method: according to the mol ratio of 1:1-10:1-10 mixing a monomer 1, a monomer 2 and a monomer 3, adding a monomer 4 with the mass 1-1.2 times of the total sum of the monomer 1, the monomer 2 and the monomer 3, adding an organic solvent, a Lewis base and a catalyst, and heating at 220 ℃ for 5 hours to react to obtain the polyaryletherketone, wherein the structure of the monomer 1 is as follows:
Figure FDA0003331467810000021
wherein R is 1 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy; r is R 2 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy;
the structure of the monomer 2 is as follows:
Figure FDA0003331467810000022
wherein R is 3 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy; r is R 4 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy; r is R 5 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy;
the structure of the monomer 3 is as follows:
Figure FDA0003331467810000023
wherein R is 6 Is one of hydrogen, hydroxyl, carboxyl, methyl or methoxy; r is R 7 Is hydrogenOne of hydroxyl, carboxyl, methyl or methoxy;
the monomer 4 is 1, 4-bis (4-fluorobenzoyl) benzene, and the structure is that
Figure FDA0003331467810000024
The organic solvent is one of benzene, toluene, dimethylformamide, dimethyl sulfoxide, n-hexane or heptane; the Lewis base is selected from one of diphenyl sulfone, sulfolane or N-methyl pyrrolidone; the catalyst is sodium carbonate or potassium carbonate.
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