CN113321786B - Sulfonic conjugated microporous polymer, preparation method and application - Google Patents
Sulfonic conjugated microporous polymer, preparation method and application Download PDFInfo
- Publication number
- CN113321786B CN113321786B CN202110594912.6A CN202110594912A CN113321786B CN 113321786 B CN113321786 B CN 113321786B CN 202110594912 A CN202110594912 A CN 202110594912A CN 113321786 B CN113321786 B CN 113321786B
- Authority
- CN
- China
- Prior art keywords
- microporous polymer
- conjugated microporous
- sulfonic acid
- sulfonic
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/145—Side-chains containing sulfur
- C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3422—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms conjugated, e.g. PPV-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/516—Charge transport ion-conductive
-
- 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 discloses a sulfonic conjugated microporous polymer, a preparation method and application thereof. The conjugated microporous polymer is formed by coupling aryl dibromide containing sulfonic groups and acetylene compounds through Sonogashira, the material structure contains abundant sulfonic acid groups, and alkali metal ions can be effectively replaced and combined through ion exchange. The sulfonic acid group site can promote cation migration, and high migration number and stable high conductivity are obtained. The sulfonic acid group conjugated microporous polymer solid electrolyte has good lithium ion conductivity and the temperature of 40 ℃ is 1.71 multiplied by 10‑4S cm‑1At 120 deg.C, it reaches 2.34X 10‑3S cm‑1The assembled solid lithium ion battery can stably run at high temperature.
Description
Technical Field
The invention belongs to the field of conjugated microporous polymers, and relates to a sulfonic conjugated microporous polymer, a preparation method and application thereof as a solid electrolyte material in the field of electrochemistry.
Background
The traditional commercial lithium ion battery has potential safety hazards such as explosion and the like due to the use of a large amount of combustible organic solvents. Solid electrolytes have received much attention because of their low flammability, high thermal stability, no leakage, low risk of explosion, and the like. The safety of the battery can be effectively improved by replacing the liquid electrolyte with the non-flammable solid electrolyte. The design and development of the solid electrolyte with high-efficiency ionic conductivity have important significance for improving the performance of the lithium ion battery.
Conjugated Microporous Polymers (CMPs) are rigid porous Polymers with a large Conjugated system formed by covalently linking Conjugated monomers having different topological sequences. As a new organic porous polymer, CMPs have the characteristics of light weight, large specific surface area, adjustable pore size structure, easy functionalization and the like, and show great application potential in the fields of gas adsorption separation, heterogeneous catalysis, energy storage, chemical sensing and the like. The document [ Sensors and activators B,2013,181,730-734] discloses a monosaccharide fluorescent switch consisting of a sulfonic conjugated microporous polymer as an anionic polyelectrolyte and a cationic tri-pyridinium quaternary ammonium salt, wherein in the switch system, the polyelectrolyte is used as a fluorescent signal unit, and pyridine boric acid is used as an acceptor and a quencher. Based on the electrostatic interaction mechanism, monosaccharide detection probes have a reversible "on-off" fluorescence response. The probe requires only a small blood sample for the detection of diabetes. At present, no sulfonic acid group conjugated microporous polymer as a solid electrolyte material is reported.
Disclosure of Invention
One of the purposes of the invention is to provide a sulfonic acid group conjugated microporous polymer with efficient ion conduction performance and electrochemical stability, wherein a functional monomer containing a sulfonic acid group is introduced into the conjugated microporous polymer structure, and the structural formula of the polymer is as follows:
The second object of the present invention is to provide a method for preparing the sulfonic acid group conjugated microporous polymer, comprising the steps of:
dissolving aryl dibromide containing sulfonic group, acetylene compound, tetrakis (triphenylphosphine) palladium catalyst and cuprous iodide catalyst in an organic solvent to obtain a mixed solution, placing the mixed solution in a nitrogen dark atmosphere at 80 +/-10 ℃ for reaction, performing suction filtration, washing, performing Soxhlet extraction, and drying to obtain the sulfonic group conjugated microporous polymer.
Preferably, the aryl dibromide containing sulfonic acid group is 1, 4-dibromo-2, 5-bis (3-sulfopropoxy) benzene.
Preferably, the acetylene compound is 1,3, 5-triacetoxybenzene or 1,3, 5-tris (4-ethynylphenyl) benzene.
Preferably, the organic solvent is a mixed solvent of toluene and triethylamine in a volume ratio of 1: 1.
Preferably, the molar ratio of the sulfonic acid group-containing aryl dibromide to the acetylene-based compound is 3: 2.
preferably, the molar amount of tetrakis (triphenylphosphine) palladium is between 3% and 5% of the total ethynyl group molar amount.
Preferably, the molar amount of cuprous iodide is 3% to 5% of the total ethynyl groups.
Preferably, the reaction time is 24h or more.
Preferably, the washing is carried out sequentially with chloroform, water, methanol, acetone.
Preferably, the Soxhlet extraction is carried out by sequentially adopting dichloromethane and methanol as solvents, and the extraction time is 24-48 h.
Preferably, the drying temperature is 60-80 ℃, and the drying time is more than 12 h.
The invention also aims to provide a sulfonic acid group conjugated microporous polymer solid electrolyte, which consists of a sulfonic acid group conjugated microporous polymer and ionic liquid, wherein the sulfonic acid group conjugated microporous polymer is used as a main body, and the ionic liquid is an ion transmission channel.
In the present invention, the ionic liquid is an ionic liquid conventionally used in the art, such as 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-n-butyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide, and the like.
Preferably, the mass ratio of the sulfonic acid group conjugated microporous polymer to the ionic liquid is 2: 1.
The fourth purpose of the invention is to provide a preparation method of the sulfonic conjugated microporous polymer solid electrolyte, which comprises the following steps:
adding the sulfonic group conjugated microporous polymer into an alkali metal ion salt solution, performing ultrasonic treatment and stirring to enable sulfonic groups to be combined with alkali metal ions for ion exchange, centrifuging, collecting solids, repeating for more than 2 times until the alkali metal ions are completely exchanged, drying, mixing the ion exchanged sulfonic group conjugated microporous polymer powder with an ionic liquid, uniformly grinding, and tabletting to obtain the solid electrolyte sheet.
In the present invention, the alkali metal ion salt is an alkali metal ion salt conventionally used in the battery field, such as a lithium salt, a sodium salt, a potassium salt, or the like.
Specifically, the lithium salt is lithium bistrifluoromethanesulfonylimide or lithium acetate, the sodium salt is sodium chloride or sodium bistrifluoromethanesulfonylimide, and the potassium salt is potassium chloride or potassium acetate.
Preferably, the solvent in the alkali metal ion salt solution is tetrahydrofuran, methanol or water.
Preferably, the concentration of the alkali metal ion salt is 1 mol/L.
The invention also provides application of the sulfonic conjugated microporous polymer solid electrolyte in a battery.
In the invention, the battery can be a lithium ion battery, a sodium ion battery or a potassium ion battery.
Specifically, taking a lithium ion battery as an example, the lithium ion battery is assembled by a sulfonic acid group conjugated microporous polymer solid electrolyte, a metallic lithium negative electrode and a lithium iron phosphate composite positive electrode. The lithium iron phosphate composite positive electrode is prepared by dispersing, coating, drying and tabletting lithium iron phosphate powder, a conductive agent, an adhesive, an ionic liquid and lithium salt according to a mass ratio of 40:5:5:2: 8.
In the present invention, the conductive agent is a conductive agent commonly used in batteries, such as Super-P. The binder is a binder commonly used in batteries, such as a solution of polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP).
Compared with the prior art, the invention has the following advantages:
the invention adopts Sonogashira coupling reaction to synthesize the sulfonic conjugated microporous polymer. The sulfonic group conjugated microporous polymer is connected through covalent bond acetylene bonds, and has high chemical stability. The sulfonic group modified on the sulfonic conjugated microporous polymer skeleton has the function of combining with cations such as lithium ions and the like, and avoids the interference of introducing multiple ions caused by the fact that a common polymer is only used as an object. At the same time, the sulfonic group is connected to a flexible chain segment structure, havingThe migration of cations is facilitated, the migration number of lithium ions is greater than 0.5, the migration number is higher than that of a common polymer electrolyte, and the electrochemical window of the electrolyte can be stabilized at 2.0-4.0V. Therefore, sulfonic acid groups are introduced into the CMPs framework, which is beneficial to the CMPs material to transmit alkali metal ions, and the obtained sulfonic acid group conjugated microporous polymer has good application in the ion conduction direction, and can be used as a solid electrolyte for an alkali metal ion solid battery. The solid electrolyte has high lithium ion conductivity of about 1.71X 10 at 40 deg.C-4Scm-1At 120 deg.C, 2.34X 10-3S cm-1. The solid lithium ion battery assembled by the solid electrolyte can provide 120.3mAh g at the current density of 0.05C -1The initial discharge specific capacity can be maintained at 101.91mAh g after 30 cycles-1The result shows that the sulfonic conjugated microporous polymer solid electrolyte has good electrochemical cycling stability.
Drawings
FIG. 1 shows the structural formula and reaction formula of sulfonic acid group conjugated microporous polymer.
FIG. 2 is a Fourier transform infrared spectrum of a sulfonic acid group conjugated microporous polymer.
FIG. 3 is a nitrogen adsorption and desorption curve of a sulfonic acid group conjugated microporous polymer.
FIG. 4 is a thermogravimetric curve of the sulfonic acid group conjugated microporous polymer prepared by the present invention under nitrogen atmosphere.
FIG. 5 is a scanning electron microscope photograph of a sulfonic acid based conjugated microporous polymer prepared according to the present invention.
FIG. 6 is a NMR spectrum of a sulfonic acid group-containing aryl dibromide of the present invention.
FIG. 7 is an electrochemical impedance spectrum of a sulfonic acid group conjugated microporous polymer solid electrolyte material according to the present invention.
FIG. 8 is a lithium ion conductivity diagram of a sulfonic acid group conjugated microporous polymer solid electrolyte material according to the present invention.
Fig. 9 is a charge-discharge curve of an assembled lithium ion battery of the present invention.
Fig. 10 is a graph of the cycling ratio capacity and efficiency of an assembled lithium ion battery of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
In the present invention, reference is made to the preparation of 1, 4-dibromo-2, 5-bis (3-sulfopropoxy) benzene [ Sensors and activators B,2013,181,730-]The synthetic route is as follows:
the method comprises the following specific steps: 2, 5-dibromo-1, 4-benzenediol (6.35g, 20.0mmol) and sodium hydroxide (2.0g, 50.0mmol) were dissolved in 200mL of water, and the reaction mixture was stirred under a nitrogen atmosphere. 1, 3-propane sultone was dissolved in 40mL dioxane and immediately added to the reaction mixture. The reaction system is stirred and reacted at room temperature overnight, and the temperature is increased to 90 ℃ and the reaction is stirred and reacted for 30 min. The reaction was cooled in an ice bath to precipitate a solid. Filter and wash the solid with ice water and acetone. The crude product was purified by secondary recrystallization from water to give 6.8g of 1, 4-dibromo-2, 5-bis (3-sulfopropoxy) benzene in 61.1% yield. The hydrogen nuclear magnetic resonance spectrum of 1, 4-dibromo-2, 5-bis (3-sulfopropoxy) benzene is shown in FIG. 6,1H NMR(300MHz,D2O)δ(ppm):7.39(s,2H),4.17(t,4H),3.12(t,4H),2.19(q,4H)。
in the present invention, the acetylene-based compound is 1,3, 5-triacetoxybenzene, and is purchased from Tianjin Xiansi.
1,3, 5-tris (4-ethynylphenyl) benzene preparation reference [ catalysis science & Technology,2015,5,2585], synthetic route is as follows:
the method comprises the following specific steps: the preparation method comprises the following steps of mixing 4,4 ' -dibromo-5 ' - (4-bromophenyl) -1,1 ': 3', 1 "-terphenyl (1.63g, 3mmol), CuI (17.14mg, 0.09mmol), triphenylphosphine (78.7mg, 0.3mmol) and Pd (PPh) 3)2Cl2(105.3mg, 0.15mmol) was dissolved in 150mL of anhydrous triethylamine under a nitrogen atmosphere. Heated to 50 ℃ and stirred for 30 minutes. Then trimethylsilyl is added dropwiseEthynylene (1.48mL, 13.5mmol) and the reaction mixture was refluxed for 36 hours. The crude product was purified by column chromatography to give 1,3, 5-tris (4-ethynyltrimethylsilylphenyl) benzene (1.25g, yield 70%). 1,3, 5-tris (4-ethynyltrimethylsilylphenyl) benzene (1.25g, 2.1mmol) was dissolved in 30mL of methylene chloride and 60mL of methanol. After stirring for 5 min, solid potassium carbonate (1.73g, 12.54mmol) was added and the reaction mixture was stirred at room temperature for 24 h. Then, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to give 1,3, 5-tris (4-ethynylphenyl) benzene (0.57g, yield 72.5%).
Example 1
The preparation method of the sulfonic conjugated microporous polymer comprises the following steps:
1, 4-dibromo-2, 5-bis (3-sulfopropoxy) benzene (834.2mg, 1.5mmol), tetrakis (triphenylphosphine) palladium (138.5mg, 0.12mmol) and cuprous iodide (22.9mg, 0.12mmol), and 1,3, 5-triethylynylbenzene (150.2mg, 1.0mmol) were dissolved in 25mL of toluene and 25mL of triethylamine under an argon atmosphere. The reaction was heated to 80 ℃ and stirred at 80 ℃ for 36 hours. After cooling to room temperature, the solid was suction filtered, washed successively with chloroform, water, methanol and acetone, and then subjected to sequential Soxhlet extraction with dichloromethane and methanol for 48 hours to remove unreacted monomers or catalyst residues. The sample was dried under vacuum at 80 ℃ for 24 hours to give 563mg of a sulfonic acid group-conjugated microporous polymer, in 76% yield.
Example 2
The preparation method of the sulfonic conjugated microporous polymer comprises the following steps:
1, 4-dibromo-2, 5-bis (3-sulfopropoxy) benzene (834.2mg, 1.5mmol), tetrakis (triphenylphosphine) palladium (138.5mg, 0.12mmol) and cuprous iodide (22.9mg, 0.12mmol), and 1,3, 5-tris (4-ethynylphenyl) benzene (378.5mg, 1.0mmol) were dissolved in 25mL of toluene and 25mL of triethylamine under an argon atmosphere. The reaction was heated to 80 ℃ and stirred at 80 ℃ for 36 hours. After cooling to room temperature, the solid was suction filtered, washed successively with chloroform, water, methanol and acetone, and then subjected to sequential Soxhlet extraction with dichloromethane and methanol for 48 hours to remove any unreacted monomer or catalyst residues. The sample was dried under vacuum at 80 ℃ for 24 hours to give 815mg of a sulfonic acid group-conjugated microporous polymer, a yield of 84%.
Fig. 1 shows a synthetic route and a structural diagram of a sulfonic acid group conjugated microporous polymer, and it can be seen that a sulfonic acid group is directly modified in the structure of a material.
FIG. 2 shows the Fourier transform infrared spectrum of the material, from which it can be seen that 1,3, 5-triethylynylbenzene is 3280cm-1Has a strong peak obviously, which is caused by the stretching of terminal alkyne-C.ident.C-H. And the Fourier infrared spectrum of the synthesized sulfonic conjugated microporous polymer almost disappears the peak of-C.ident.C-H, which indicates that the reaction is successfully polymerized.
FIG. 3 shows a nitrogen adsorption-desorption curve of a sulfonic acid group-conjugated microporous polymer, and it can be seen that the material exhibits an I-type adsorption curve, indicating the microporous characteristics of the material, whose BET specific surface area is 287m2 g-1。
Fig. 4 shows a thermogravimetric curve of the sulfonic acid group conjugated microporous polymer in a nitrogen atmosphere, and it can be seen that the material has high thermal stability with almost no mass loss until 350 ℃.
Figure 5 shows a scanning electron microscope of a sulfonic acid based conjugated microporous polymer showing the lamellar structure of the material.
Example 3: preparation of sulfonic conjugated microporous polymer solid electrolyte and alternating current impedance test
1) Preparing a sulfonic conjugated microporous polymer solid electrolyte: 100mg of sulfonic group conjugated microporous polymer powder is added into 20mL of 1 mol/L lithium bistrifluoromethanesulfonylimide solution, ultrasonic treatment is carried out for 5min, and stirring is carried out for one day. Centrifugation was carried out at 10000rpm, and the solid was collected. Repeating the operation for three times until the alkali metal ion exchange is complete, and drying at 80 ℃ overnight; 6mg of the sulfonic conjugated microporous polymer powder after ion exchange and 3mg of 1-butyl-3-methylimidazol bis (trifluoromethylsulfonyl) imide are ground for 10min, and the mixed powder is subjected to pressure maintaining at 5MPa for 0.5h and pressed into a solid electrolyte sheet with the diameter of 5mm and the thickness of 0.253 mm.
In the present invention, the alkali metal ion salt is an alkali metal ion salt commonly used in a battery electrolyte, and may be a lithium salt, a sodium salt, a potassium salt, and the like, specifically, a lithium salt such as lithium bistrifluoromethanesulfonylimide and lithium acetate, a sodium salt such as sodium chloride and sodium bistrifluoromethanesulfonylimide, and a potassium salt such as potassium chloride and potassium acetate. The invention is only represented by the lithium bistrifluoromethanesulfonylimide as an example, and other alkali metal ion salts can be conventionally replaced.
In the present invention, the ionic liquid is an ionic liquid conventionally used in the art, such as 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-n-butyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide, etc., and only 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide is taken as a representative example.
2) Electrochemical alternating-current impedance test of the sulfonic conjugated microporous polymer solid electrolyte: the temperature-changing alternating-current impedance test is carried out by adopting a Biological SP-200 portable workstation, the test temperature range is 40-120 ℃, the frequency range is 7MHz-0.1Hz, and the amplitude voltage is 10 mV.
The ac impedance spectra of the sulfonic acid group conjugated microporous polymer solid electrolyte material at different temperatures in this example are shown in fig. 7; the lithium ion conductivity of the solid electrolyte material is shown in FIG. 8, and the ion conductivity of the material at 40 ℃ is about 1.71X 10 by conversion -4S cm-1At 120 deg.C to 2.34X 10-3S cm-1。
Example 4: lithium ion battery prepared from sulfonic conjugated microporous polymer solid electrolyte and electrochemical performance test thereof
1) Preparing a lithium iron phosphate composite anode of the lithium ion battery: weighing lithium iron phosphate powder, Super-P, polyvinylidene fluoride (PVDF), ionic liquid and lithium bis (trifluoromethanesulfonyl) imide according to the mass ratio of 40:5:5:2:8, grinding for 15min, dropwise adding a proper amount of N-methylpyrrolidone, then magnetically stirring for 6h to form uniform slurry, uniformly coating the slurry on an aluminum foil current collector by using a scraper, carrying out vacuum drying at 110 ℃ for 40min, and punching into a wafer with the diameter of 5mm by using a die to obtain the lithium iron phosphate composite positive plate.
2) Assembling the lithium ion button battery: the lithium ion battery is formed by assembling a sulfonic conjugated microporous polymer solid electrolyte, a lithium metal cathode and a lithium iron phosphate composite anode in a glove box with the water oxygen content lower than 0.5 ppm. And (4) carrying out electrochemical performance test after heat preservation for 6h at 100 ℃.
3) And (3) electrochemical performance testing: the lithium ion battery is subjected to high-temperature (100 ℃) constant-current charge and discharge performance test.
FIG. 9 shows that solid-state lithium-ion batteries can provide up to 120.3mAh g at a current density of 0.05C -1The initial discharge specific capacity of the lithium ion battery can still maintain 101.91mAh g after 30 cycles of circulation-1The result shows that the sulfonic conjugated microporous polymer solid electrolyte has good electrochemical cycling stability.
Specific embodiments of the present invention have been described in detail above. It should be understood that the above examples are only for the purpose of clarity of illustration and are not intended to limit the embodiments, and that those skilled in the art can make various changes or modifications within the scope of the appended claims without affecting the essence of the present invention.
Claims (10)
1. The sulfonic conjugated microporous polymer is characterized in that the structural formula is as follows:
2. the method of preparing a sulfonic acid based conjugated microporous polymer according to claim 1, comprising the steps of:
dissolving aryl dibromide containing sulfonic group, acetylene compound, tetrakis (triphenylphosphine) palladium catalyst and cuprous iodide catalyst in an organic solvent to obtain a mixed solution, placing the mixed solution in a nitrogen dark atmosphere at 80 +/-10 ℃ for reaction, performing suction filtration, washing, performing Soxhlet extraction, and drying to obtain the sulfonic group conjugated microporous polymer.
3. The production method according to claim 2, wherein the sulfonic acid group-containing aryl dibromide is 1, 4-dibromo-2, 5-bis (3-sulfopropoxy) benzene; the acetylene compound is 1,3, 5-triacetoxybenzene or 1,3, 5-tri (4-ethynylphenyl) benzene; the organic solvent is a mixed solvent of toluene and triethylamine in a volume ratio of 1: 1; the molar ratio of the aryl dibromide containing sulfonic acid groups to the acetylene-based compound is 3: 2; the molar weight of the tetrakis (triphenylphosphine) palladium accounts for 3-5% of the molar weight of the total ethynyl groups, and the molar weight of the cuprous iodide accounts for 3-5% of the molar weight of the total ethynyl groups; the reaction time is more than 24 h; washing with chloroform, water, methanol and acetone in sequence; sequentially adopting dichloromethane and methanol as solvents to perform Soxhlet extraction for 24-48 h; the drying temperature is 60-80 ℃, and the drying time is more than 12 h.
4. A sulfonic acid group-conjugated microporous polymer solid electrolyte comprising the sulfonic acid group-conjugated microporous polymer according to claim 1 and an ionic liquid.
5. The sulfonic acid group conjugated microporous polymer solid electrolyte according to claim 4, wherein the ionic liquid is 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide or 1-n-butyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide, and the mass ratio of the sulfonic acid group conjugated microporous polymer to the ionic liquid is 2: 1.
6. The method for preparing a sulfonic acid based conjugated microporous polymer solid electrolyte according to claim 5, comprising the steps of:
adding the sulfonic group conjugated microporous polymer into an alkali metal ion salt solution, performing ultrasonic treatment and stirring to enable sulfonic groups to be combined with alkali metal ions for ion exchange, centrifuging, collecting solids, repeating for more than 2 times until the alkali metal ions are completely exchanged, drying, mixing the ion exchanged sulfonic group conjugated microporous polymer powder with an ionic liquid, uniformly grinding, and tabletting to obtain the solid electrolyte sheet.
7. The method of claim 6, wherein the alkali metal ion salt is a lithium salt, a sodium salt, or a potassium salt; the lithium salt is lithium bistrifluoromethane sulfonyl imide or lithium acetate, the sodium salt is sodium chloride or bistrifluoromethane sulfonyl imide sodium, and the potassium salt is potassium chloride or potassium acetate; the solvent in the alkali metal ion salt solution is tetrahydrofuran, methanol or water; the concentration of the alkali metal ion salt is 1 mol/L.
8. Use of the sulfonic acid based conjugated microporous polymer solid electrolyte according to claim 4 in a battery.
9. The use according to claim 8, wherein the battery is a lithium ion battery, a sodium ion battery or a potassium ion battery.
10. The application of claim 8, wherein the lithium ion battery is assembled by a sulfonic acid group conjugated microporous polymer solid electrolyte, a metallic lithium cathode and a lithium iron phosphate composite anode; the lithium iron phosphate composite positive electrode is prepared by dispersing, coating, drying and tabletting lithium iron phosphate powder, a conductive agent, an adhesive, an ionic liquid and a lithium salt according to a mass ratio of 40:5:5:2: 8; the conductive agent is Super-P; the binder is a solution of polyvinylidene fluoride in N-methyl pyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110594912.6A CN113321786B (en) | 2021-05-28 | 2021-05-28 | Sulfonic conjugated microporous polymer, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110594912.6A CN113321786B (en) | 2021-05-28 | 2021-05-28 | Sulfonic conjugated microporous polymer, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113321786A CN113321786A (en) | 2021-08-31 |
| CN113321786B true CN113321786B (en) | 2022-06-28 |
Family
ID=77422408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110594912.6A Active CN113321786B (en) | 2021-05-28 | 2021-05-28 | Sulfonic conjugated microporous polymer, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113321786B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845773B (en) * | 2021-10-09 | 2023-05-05 | 绍兴道普新材料科技有限公司 | Sulfonic group doped microporous polyphenyl/polypyrrole composite material, and preparation method and application thereof |
| CN114069044B (en) * | 2021-10-27 | 2023-06-13 | 珠海冠宇电池股份有限公司 | Positive electrode material and lithium ion battery containing same |
| CN114920909A (en) * | 2022-06-06 | 2022-08-19 | 青海大学 | Aryl boron-anthraquinone based conjugated polymer and preparation method and application thereof |
| CN115449055B (en) * | 2022-09-23 | 2023-10-27 | 南京理工大学 | Conjugated microporous polymer and application thereof as solid electrolyte in lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827353A (en) * | 2011-06-17 | 2012-12-19 | 中国科学院大连化学物理研究所 | Synthesis method of spherical organic conjugated polymer |
| CN110016126A (en) * | 2019-03-04 | 2019-07-16 | 华南理工大学 | A kind of conjugation microporous polymer and the preparation method and application thereof |
| CN111454436A (en) * | 2020-04-27 | 2020-07-28 | 齐齐哈尔大学 | Preparation method of chiral conjugated microporous polymer containing (S) -N-sec-butylacetamide |
-
2021
- 2021-05-28 CN CN202110594912.6A patent/CN113321786B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827353A (en) * | 2011-06-17 | 2012-12-19 | 中国科学院大连化学物理研究所 | Synthesis method of spherical organic conjugated polymer |
| CN110016126A (en) * | 2019-03-04 | 2019-07-16 | 华南理工大学 | A kind of conjugation microporous polymer and the preparation method and application thereof |
| CN111454436A (en) * | 2020-04-27 | 2020-07-28 | 齐齐哈尔大学 | Preparation method of chiral conjugated microporous polymer containing (S) -N-sec-butylacetamide |
Non-Patent Citations (3)
| Title |
|---|
| Chiral Conjugated Microporous Polymers as Novel Chiral Fluorescence Sensors for Amino Alcohols;Wei, J;《MACROMOLECULAR CHEMISTRY AND PHYSICS》;20131030;第214卷(第19期);2232-2238 * |
| Fluorescence Response of Conjugated Polyelectrolyte in an Immiscible Two-Phase System via Nonelectrostatic Interaction with Surfactants;Kim, BSI;《ACS APPLIED MATERIALS & INTERFACES》;20150624;第7卷(第24期);13701-13706 * |
| 新型共轭微孔聚合物的制备及其性能研究;包璐璐;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20170115;B016-29 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113321786A (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113321786B (en) | Sulfonic conjugated microporous polymer, preparation method and application | |
| Chen et al. | Lithium salt of tetrahydroxybenzoquinone: toward the development of a sustainable Li-ion battery | |
| CN113512033B (en) | Phenoxazine and phenothiazine covalent triazine framework material, and preparation method and application thereof | |
| CN110534711B (en) | Preparation method of polyimide composite material and application of polyimide composite material in battery | |
| CN110964198A (en) | Polyimide material and preparation method and application thereof | |
| Li et al. | A laterally extended perylene hexacarboxylate via Diels-Alder reaction for high-performance organic lithium-ion batteries | |
| CN108461752B (en) | Triphenylamine polymer with side chain having conjugated carbonyl compound, preparation and application thereof | |
| CN104409735A (en) | Ferrocene group-containing aniline derivative polymer and use thereof | |
| CN115232326A (en) | Metal organic framework material, preparation thereof and application thereof in electrode material | |
| CN108623787B (en) | Novel conjugated microporous organic polymer and synthesis and application thereof | |
| CN110590789B (en) | Nitrogen-rich triphenylamine derivative conjugated polymer material and preparation and application of monomer thereof | |
| CN115557955B (en) | Hexaazatrinaphthalene monomer and preparation method thereof, porous organic polymer and preparation method and application thereof | |
| CN115109235B (en) | Imidazole group functionalized polymer and preparation method and application thereof | |
| CN111211327B (en) | Compound for lithium ion battery anode material and preparation method and application thereof | |
| CN114069044B (en) | Positive electrode material and lithium ion battery containing same | |
| CN112072062B (en) | Multi-carbonyl aza-condensed ring material for proton battery and preparation method of electrode thereof | |
| CN111704717B (en) | Novel organic negative electrode material of sodium ion battery based on azo polyimide | |
| CN107644996B (en) | Preparation method of pure organic polymer lithium ion battery electrode material | |
| CN115353471B (en) | Organic electrode material of anthroquinone polymer, and preparation method and application thereof | |
| CN112694613B (en) | Polyimide material, preparation method thereof and application thereof in alkali metal ion battery | |
| CN114957578B (en) | Covalent organic framework material based on thienyl and oxazinyl, and preparation method and application thereof | |
| CN112111061B (en) | Preparation method of polyimide and application of polyimide in water-based lithium ion battery | |
| CN114874211B (en) | Imide derivative, preparation method and application thereof in flow battery | |
| CN109705343B (en) | Azulenyl covalent triazine skeleton and application thereof | |
| CN115850697A (en) | Pyrene tetraone-based triazine covalent organic framework material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |