CN115572464B - Multi-piperidine functionalized anion exchange membrane, preparation method and application thereof in neutral organic flow battery - Google Patents
Multi-piperidine functionalized anion exchange membrane, preparation method and application thereof in neutral organic flow battery Download PDFInfo
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000007935 neutral effect Effects 0.000 title abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 239000012528 membrane Substances 0.000 claims abstract description 27
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 claims abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 13
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 229930184652 p-Terphenyl Natural products 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 9
- 238000005956 quaternization reaction Methods 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
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Abstract
The invention belongs to the technical field of alkaline anion exchange membranes, and provides a multi-piperidine functionalized anion exchange membrane, a preparation method and application thereof in a neutral organic flow battery, and the introduced benzhydryl amine contains hydrophilic amino groups, can assist in forming hydrophilic channels, relieves the rigidity of a main chain by methine among benzene rings, and also promotes microphase separation: a polymer containing a multi-piperidine functional group having excellent conductivity, ion selectivity and dimensional stability is synthesized. The prepared membrane has good dimensional stability and good ionic conductivity, and has excellent performance in a neutral flow battery.
Description
Technical Field
The invention belongs to the technical field of alkaline anion exchange membranes, and relates to a multi-piperidine functionalized anion exchange membrane, a preparation method and application thereof in a neutral organic flow battery.
Background
Energy storage devices are necessary for stable output of solar and wind energy. Redox Flow Batteries (RFBs) are attracting attention for their long life, high efficiency and safety. Among the RFBs of many types, the full-vanadium redox flow battery process is the most mature, but the strong acid system is easy to cause corrosion of equipment, and the cost of adopting inorganic vanadium ions as active substances is too high, so that the development of the full-vanadium redox flow battery is limited. The neutral organic flow battery (NAORFB) adopts small organic molecules as active substances, the cost of the organic liquid flow battery can be controlled by adjusting the preparation process of the small organic molecules, and the neutral system can not cause serious corrosion problems, so that the industrial maintenance cost is saved. The membrane is a core component of NAORFB, which not only blocks cross-contamination of bipolar active substances, but also allows chloride ions to shuttle back and forth between the anode and cathode as carriers to achieve a closed circuit. Leo Liu indicates on journal Journal of Materials A that the membrane resistance in NAORFB is 70% of the total cell resistance and that the author Xiao tests commercial cathode membrane AMVN on journal Journal of Membrane Science, which indicates that the AMVN chloride ion conductivity is low. It is therefore one of the hot spots of current interest to find anion exchange membranes with high chloride conductivity, high stability and low cost.
Disclosure of Invention
The invention aims to improve the ion transfer performance and the dimensional stability of an anion exchange membrane, and provides a preparation method of a polyamine functionalized anion exchange membrane, which comprises the following steps: a polyamine-functionalized polymer with good dimensional stability and mechanical properties is synthesized, and then the polymer is quaternized to obtain the polyamine-functionalized anion exchange membrane. The introduced benzhydryl amine contains hydrophilic amino groups, can assist the formation of hydrophilic channels, and the methine between benzene rings relieves the rigidity of a main chain and promotes microphase separation. The prepared membrane has good dimensional stability and good ionic conductivity, and has excellent performance when applied to a neutral flow battery.
The technical scheme of the invention is as follows:
the introduced benzhydrylamine contains hydrophilic amino groups, can assist the formation of hydrophilic channels, and the methine between benzene rings relieves the rigidity of a main chain and promotes microphase separation; the structural formula is as follows:
wherein: 0< x <1.
A method for preparing a multi-piperidine functional anion-exchange membrane, which comprises the following steps:
(1) Synthesis of aryl Ether-free Polymer PPApi-x: adding p-terphenyl, diphenyl methylamine and 1-methyl-4-piperidone into dichloromethane, adding trifluoroacetic acid and trifluoromethanesulfonic acid at 0-5 ℃ for reaction for 4-5 hours at 0-5 ℃ to obtain viscous liquid; slowly pouring the liquid into anhydrous methanol to obtain a white fibrous polymer, carrying out suction filtration and water washing for 24 hours, and drying in a 60 ℃ oven for 48 hours;
the mol ratio of the p-terphenyl, the benzhydryl amine and the 1-methyl-4-piperidone is 9-1:1-9:10;
the molar ratio of the 1-methyl-4-piperidone to the trifluoroacetic acid is 0.7:1;
the molar ratio of the 1-methyl-4-piperidone to the trifluoromethanesulfonic acid is 1:8.3;
the ratio of the 1-methyl-4-piperidone to the dichloromethane is 4.11 mmol/3 mL;
(2) Quaternization of the aryl ether-free polymer QPPApi-x: taking the polymer PPApi-x obtained in the step (1), heating and dissolving in DMSO, adding 6-piperidine ionic liquid and potassium carbonate, and reacting for 15h at a certain temperature; after the reaction is finished, pouring the solution into ethyl acetate to separate out, filtering and washing with water, and drying at 60 ℃ for 48 hours;
the molar ratio of PPApi-x to 6-piperidine ionic liquid is 1:3;
the molar ratio of PPApi-x to potassium carbonate is 1:3;
the addition ratio of PPApi-x to DMSO is 1g:10mL;
(3) Preparation of a multifunctional piperidine functional ion exchange membrane: dissolving the aryl ether-free polymer QPapi-x synthesized in the step (2) in DMSO, transferring the dissolved aryl ether-free polymer QPapi-x into a film casting glass plate, placing the film casting glass plate in an oven for film casting, and completely volatilizing the solvent to obtain a film material; soaking the membrane in sodium chloride solution at room temperature for 24 hours to enable the membrane to perform sufficient ion exchange;
the addition ratio of QPapi-x to DMSO is 0.10-0.15 g/5 mL.
Further, the drying temperature of the film formed by the casting method is 60-80 ℃ and the time is 48 hours.
Further, in the step (2), the reaction temperature is 50 ℃.
The invention has the effects and benefits that the polyamine functionalized anion exchange membrane applied to the neutral flow battery is designed and prepared through condensation and quaternization reactions. The ionic conductivity of the membrane can be effectively improved by introducing a plurality of quaternary ammonium, and the introduction of hydrophilic amino groups can assist in forming good microphase separation channels, so that the membrane has higher ionic conductivity. The multi-ammonium functional anion exchange membrane prepared by the method can show very excellent battery performance, the energy efficiency of the multi-ammonium functional anion exchange membrane is far better than that of common membranes such as AMVN and the like, the multi-ammonium functional anion exchange membrane has very good stability, and the efficiency of the multi-ammonium functional anion exchange membrane after 1000 cycles of battery circulation is not obviously attenuated.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum: (a) a ppapix polymer; (b) QPPApi-x polymer; (c) FTIR profile of QPapi-x membranes.
Fig. 2 is a graph of membrane cell performance for three examples at different densities: (a) CE, (b) VE, and (c) EE.
FIG. 3 is 40mA/cm 2 Battery cycle test pattern for example 1 film.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, but the embodiments of the present invention are not limited thereto.
Example 1 (x=0.5)
(1) Synthesis of aryl ether-free Polymer: 0.43g of p-terphenyl, 0.35g of diphenyl methylamine and 0.47g of 1-methyl-4-piperidone are weighed and transferred into 3mL of dichloromethane, 0.45mL of trifluoroacetic acid and 3mL of trifluoromethanesulfonic acid are added under ice bath condition to react for 4-5 hours to obtain viscous liquid, the liquid is slowly poured into anhydrous methanol to obtain white fibrous polymer, the white fibrous polymer is filtered by suction and washed with water for 24 hours, and dried in an oven at 60 ℃ for 48 hours, and the nuclear magnetic spectrum of the polymer is shown in a graph (a) of fig. 1.
(2) Quaternization of the polypiperidine-functionalized polymer: 0.25g of the polymer obtained in the step (1) was added to 5mL of DMSO and dissolved to form a transparent solution, and then 0.543g of 6-piperidine and 0.509g of potassium carbonate were added to react at 50℃for 15 hours. After the reaction is completed, the solution is poured into ethyl acetate to be separated out, suction filtration and water washing are carried out, the solution is dried at 60 ℃ for 48 hours, the magnetic spectrum of the functionalized polymer core is shown as a figure 1 (b), and the infrared spectrum is shown as a figure 1 (c).
(3) Preparation of a multifunctional piperidine-functionalized anion-exchange membrane: taking 0.14g of the polymer synthesized in the step (2), dissolving in 5mL of DMSO, pouring into a 5cm multiplied by 5cm glass plate after the dissolution is completed, placing into an oven for casting, and obtaining a film after the completion of the dissolution. The membrane was immersed in a sodium chloride solution at room temperature for 24 hours to allow sufficient ion exchange.
The test shows that the ion conductivity of the multi-ammonium functional polymer anion exchange membrane prepared in the example is 19.4mS cm at 25 DEG C -1 The salt absorption rate was 39.6% and the swelling degree was 16.8%. In neutral flow batteries, 40mA cm -2 At the time of electric sealing, CE is 97.52% (shown in FIG. 2 (a)), and EE is 88.40% (shown in FIG. 2 (c); the film prepared in this example was subjected to a temperature of 40mA/cm 2 The battery cycle test was performed under the condition that the battery performance did not change significantly after 1000 times of charge and discharge, as shown in fig. 3.
Example 2 (x=0.4)
(1) Synthesis of aryl ether-free Polymer: 0.52g of p-terphenyl, 0.27g of diphenyl methylamine and 0.47g of 1-methyl-4-piperidone are weighed, transferred into 3mL of dichloromethane, added with 0.45mL of trifluoroacetic acid and 3mL of trifluoromethanesulfonic acid under ice bath condition for reaction for 4-5 hours to obtain viscous liquid, the liquid is slowly poured into anhydrous methanol to obtain white fibrous polymer, the white fibrous polymer is filtered by suction and washed with water for 24 hours, and dried in an oven at 60 ℃ for 48 hours.
(2) Quaternization of the polypiperidine-functionalized polymer: 0.25g of the polymer obtained in the step (1) is added into 5mL of DMSO, dissolved to form a transparent solution, and then 0.551g of 6-piperidine and 0.516g of potassium carbonate are added for reaction at 50 ℃ for 15h. After the reaction was completed, the solution was poured into ethyl acetate to precipitate, suction-filtered and washed with water, and dried at 60℃for 48 hours.
(3) Preparation of a multifunctional piperidine-functionalized anion-exchange membrane: taking 0.14g of the polymer synthesized in the step (2), dissolving in 5mL of DMSO, pouring into a 5cm multiplied by 5cm glass plate after the dissolution is completed, placing into an oven for casting, and obtaining a film after the completion of the dissolution. The membrane was immersed in a sodium chloride solution at room temperature for 24 hours to allow sufficient ion exchange.
The polyamine functionalized polymer anion exchange membrane prepared in this example has an ionic conductivity of 15.45mS cm at 25℃as demonstrated by testing -1 The salt absorption rate is 38.40% and the swelling degree is 23.40%. In neutral flow batteries, 40mA cm -2 At the time of the electric seal, CE was 98.15% (as shown in FIG. 2 (a)), and EE was 88.75% (as shown in FIG. 2 (c).
Example 3 (x=0.3)
(1) Synthesis of aryl ether-free Polymer: 0.61g of p-terphenyl, 0.21g of diphenyl methylamine and 0.47g of 1-methyl-4-piperidone are weighed, transferred into 3mL of dichloromethane, added with 0.45mL of trifluoroacetic acid and 3mL of trifluoromethanesulfonic acid under ice bath condition for reaction for 4-5 hours to obtain viscous liquid, the liquid is slowly poured into anhydrous methanol to obtain white fibrous polymer, the white fibrous polymer is filtered by suction and washed with water for 24 hours, and dried in an oven at 60 ℃ for 48 hours.
(2) Quaternization of the polypiperidine-functionalized polymer: 0.25g of the polymer obtained in the step (1) was added to 5mL of DMSO and dissolved to form a transparent solution, and then 0.559g of 6-piperidine and 0.523g of potassium carbonate were added to react at 50℃for 15 hours. After the reaction was completed, the solution was poured into ethyl acetate to precipitate, suction-filtered and washed with water, and dried at 60℃for 48 hours.
(3) Preparation of a multifunctional piperidine-functionalized anion-exchange membrane: taking 0.14g of the polymer synthesized in the step (2), dissolving in 5mL of DMSO, pouring into a 5cm multiplied by 5cm glass plate after the dissolution is completed, placing into an oven for casting, and obtaining a film after the completion of the dissolution. The membrane was immersed in a sodium chloride solution at room temperature for 24 hours to allow sufficient ion exchange.
The polyamine functionalized polymer anion exchange membrane prepared in this example has an ionic conductivity of 12.24mS cm at 25℃as demonstrated by testing -1 The salt absorption rate is 36.96% and the swelling degree is 15.40%. In neutral flow batteries, 40mA cm -2 At the time of the electric seal, CE was 98.01% (as shown in FIG. 2 (a)), and EE was 87.17% (as shown in FIG. 2 (c)).
Example 4 (x=0.6)
(1) Synthesis of aryl ether-free Polymer: 0.34g of p-terphenyl, 0.41g of diphenyl methylamine and 0.47g of 1-methyl-4-piperidone are weighed, transferred into 3mL of dichloromethane, added with 0.45mL of trifluoroacetic acid and 3mL of trifluoromethanesulfonic acid under ice bath condition for reaction for 4-5 hours to obtain a more viscous liquid, the liquid is slowly poured into anhydrous methanol to obtain white powdery polymer, the white powdery polymer is filtered by suction and washed with water for 24 hours, and dried in an oven at 60 ℃ for 48 hours.
(2) Quaternization of the polypiperidine-functionalized polymer: 0.25g of the polymer obtained in the step (1) is added into 5mL of DMSO, dissolved to form a transparent solution, and then 0.565g of 6-piperidine and 0.523g of potassium carbonate are added for reaction at 50 ℃ for 15h. After the reaction was completed, the solution was poured into ethyl acetate to precipitate, suction-filtered and washed with water, and dried at 60℃for 48 hours.
(3) Preparation of a multifunctional piperidine-functionalized anion-exchange membrane: taking 0.14g of the polymer synthesized in the step (2), dissolving in 5mL of DMSO, pouring into a 5cm multiplied by 5cm glass plate after the dissolution is completed, placing into an oven for casting, and obtaining a film after the completion of the dissolution. The membrane was immersed in a sodium chloride solution at room temperature for 24 hours to allow sufficient ion exchange.
The polyamine functionalized polymer anion exchange membrane prepared in this example has an ionic conductivity of 12.10mS cm at 25℃as demonstrated by testing -1 Comparable to example 1, but with a salt absorption of 45.20% and a swelling degree of 25.40%, too much swelling degree reduces the mechanical properties of the membrane, limiting the practical use of the membrane. Continuing to increase the content of benzhydrylamine can cause excessive water absorption swelling of the membrane, limiting the use of the membrane.
Example 5 (x=0)
(1) Synthesis of aryl ether-free Polymer: 0.68g of p-terphenyl and 0.47g of 1-methyl-4-piperidone are weighed and transferred into 3mL of dichloromethane, 0.45mL of trifluoroacetic acid and 3mL of trifluoromethanesulfonic acid are added under ice bath, the mixture is reacted for 4 to 5 hours under ice bath condition to obtain a more viscous liquid, the liquid is slowly poured into anhydrous methanol to obtain white powdery polymer, the white powdery polymer is filtered by suction and washed with water for 24 hours, and the polymer is dried in an oven at 60 ℃ for 48 hours.
(2) Quaternization of the polypiperidine-functionalized polymer: 0.25g of the polymer obtained in the step (1) is added into 5mL of DMSO, dissolved to form a transparent solution, and then 0.562g of 6-piperidine and 0.523g of potassium carbonate are added for reaction at 50 ℃ for 15h. After the reaction was completed, the solution was poured into ethyl acetate to precipitate, suction-filtered and washed with water, and dried at 60℃for 48 hours.
(3) Preparation of a multifunctional piperidine-functionalized anion-exchange membrane: taking 0.14g of the polymer synthesized in the step (2), dissolving in 5mL of DMSO, pouring into a 5cm multiplied by 5cm glass plate after the dissolution is completed, placing into an oven for casting, and obtaining a film after the completion of the dissolution. The membrane was immersed in a sodium chloride solution at room temperature for 24 hours to allow sufficient ion exchange.
The polyamine functionalized polymer anion exchange membrane prepared in this example has an ionic conductivity of 9.25mS cm at 25℃as demonstrated by testing -1 Below examples 1-3, the salt absorption was 34.20% and the swelling was 12%, thus confirming that the presence of hydrophilic amine groups increased the salt absorption of the membrane and thus the conductivity of the membrane.
Claims (4)
1. A multi-piperidine functionalized anion exchange membrane characterized in that the structural formula of the multi-piperidine functionalized polymer in the exchange membrane is as follows:
wherein: 0< x <1.
2. A method for preparing a multi-piperidine functional anion-exchange membrane, which is characterized by comprising the following steps:
(1) Synthesis of aryl Ether-free Polymer PPApi-x: adding p-terphenyl, diphenyl methylamine and 1-methyl-4-piperidone into dichloromethane, adding trifluoroacetic acid and trifluoromethanesulfonic acid at 0-5 ℃ for reaction for 4-5 hours at 0-5 ℃ to obtain viscous liquid; slowly pouring the liquid into anhydrous methanol to obtain a white fibrous polymer, carrying out suction filtration and water washing for 24 hours, and drying in a 60 ℃ oven for 48 hours;
the mol ratio of the p-terphenyl, the benzhydryl amine and the 1-methyl-4-piperidone is 9-1:1-9:10;
the molar ratio of the 1-methyl-4-piperidone to the trifluoroacetic acid is 0.7:1;
the molar ratio of the 1-methyl-4-piperidone to the trifluoromethanesulfonic acid is 1:8.3;
the ratio of the 1-methyl-4-piperidone to the dichloromethane is 4.11 mmol/3 mL;
(2) Quaternization of the aryl ether-free polymer QPPApi-x: taking the polymer PPApi-x obtained in the step (1), heating and dissolving in DMSO, adding 6-piperidine ionic liquid and potassium carbonate, and reacting for 15h at a certain temperature; after the reaction is finished, pouring the solution into ethyl acetate to separate out, filtering and washing with water, and drying at 60 ℃ for 48 hours;
the molar ratio of PPApi-x to 6-piperidine ionic liquid is 1:3;
the molar ratio of PPApi-x to potassium carbonate is 1:3;
the addition ratio of PPApi-x to DMSO is 1g:10mL;
(3) Preparation of a multifunctional piperidine functional ion exchange membrane: dissolving the aryl ether-free polymer QPapi-x synthesized in the step (2) in DMSO, transferring the dissolved aryl ether-free polymer QPapi-x into a film casting glass plate, placing the film casting glass plate in an oven for film casting, and completely volatilizing the solvent to obtain a film material; soaking the membrane in sodium chloride solution at room temperature for 24 hours to enable the membrane to perform sufficient ion exchange;
the addition ratio of QPapi-x to DMSO is 0.10-0.15 g/5 mL.
3. The preparation method according to claim 2, wherein the drying temperature of the film formed by the casting method is 60-80 ℃ and the time is 48 hours.
4. The process of claim 2, wherein in step (2), the reaction temperature is 50 ℃.
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