CN115572464A - 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 17
- 230000007935 neutral effect Effects 0.000 title abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 64
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 claims abstract description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 60
- 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
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 20
- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 15
- 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 14
- 239000011521 glass Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 229930184652 p-Terphenyl Natural products 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 125000003118 aryl group Chemical group 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
- 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 8
- 238000005956 quaternization reaction Methods 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 150000008378 aryl ethers Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 4
- 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 4
- 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
- 150000003839 salts Chemical class 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000022131 cell cycle Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001412 amines Chemical group 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
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 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
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
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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
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
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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
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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, wherein the introduced benzhydrylamine contains hydrophilic amino and can assist the formation of a hydrophilic channel, and the methine between benzene rings relieves the rigidity of a main chain and promotes microphase separation: a polypiperidine-containing functionalized polymer having excellent conductivity, ion selectivity and dimensional stability is synthesized. The prepared membrane has good dimensional stability and ion 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
The energy storage device is necessary for stabilizing the output solar energy and wind energy. Redox Flow Batteries (RFBs) are of interest for their long life, high efficiency and safety. Among the numerous types of RFBs, the all-vanadium flow battery is the most mature in process, but the strong acid system thereof is easy to cause corrosion of equipment, and the cost of adopting inorganic vanadium ions as active materials is too high, which limits the development of the all-vanadium flow battery. The neutral organic flow cell (NAORFB) adopts small organic molecules as active substances, the cost can be controlled by adjusting the preparation process of the small organic molecules, and the neutral system does not cause serious corrosion problems, thereby saving the maintenance cost of industry. The membrane is a core component of the NAORFB, which not only blocks cross contamination of bipolar active substances, but also allows chloride ions to shuttle back and forth between the cathode and the anode as carriers to realize a closed loop. Leo Liu, journal of Materials a, indicated that the resistance of the Membrane in NAORFB accounted for 70% of the total cell resistance, and the authors Xiao, journal of Membrane Science, tested the commercial negative Membrane AMVN and showed a lower AMVN chloride ion conductivity. Therefore, the search for anion exchange membranes with high chloride ion conductivity, high stability and low cost is one of the hot spots of current interest.
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 having good dimensional stability and mechanical properties is synthesized and then quaternized to obtain a polyamine-functionalized anion exchange membrane. The introduced benzhydrylamine contains hydrophilic amino, can assist the formation of a hydrophilic channel, and the methine among benzene rings relieves the rigidity of a main chain and also promotes microphase separation. The prepared membrane has better dimensional stability and better ionic conductivity, and has better performance when being applied to a neutral flow battery.
The technical scheme of the invention is as follows:
a multi-piperidine functionalized anion exchange membrane, the introduced benzhydrylamine contains hydrophilic amino, can assist the formation of a hydrophilic channel, and methine among benzene rings relieves the rigidity of a main chain and also promotes microphase separation; the structural formula is as follows:
wherein: 0-and x-are woven as a bundle of 1.
A preparation method of a multi-piperidine functionalized anion exchange membrane comprises the following preparation steps:
(1) Synthesis of aryl Ether free Polymer PPPii-x: adding p-terphenyl, diphenyl methylamine and 1-methyl-4-piperidone into dichloromethane, adding trifluoroacetic acid and trifluoromethanesulfonic acid at 0-5 ℃, and reacting at 0-5 ℃ for 4-5h to obtain viscous liquid; slowly pouring the liquid into anhydrous methanol to obtain a white fibrous polymer, performing suction filtration, washing with water for 24 hours, and drying in an oven at 60 ℃ for 48 hours;
the mol ratio of the p-terphenyl to the benzhydrylamine to the 1-methyl-4-piperidone is 9-1 to 10;
the molar ratio of the 1-methyl-4-piperidone to the trifluoroacetic acid is 0.7;
the molar ratio of the 1-methyl-4-piperidone to the trifluoromethanesulfonic acid is 1;
the ratio of the 1-methyl-4-piperidone to the dichloromethane is 4.11mmol;
(2) Quaternization of aryl ether-free polymer QPPApi-x: taking the polymer PPPii-x obtained in the step (1), heating and dissolving the polymer PPPii-x 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 for precipitation, carrying out suction filtration and washing with water, and drying at 60 ℃ for 48 hours;
the molar ratio of the PPPix-x to the 6-piperidine ionic liquid is 1;
the molar ratio of PPPi-x to potassium carbonate is 1;
the adding ratio of the PPPi-x to the DMSO is 1g;
(3) Preparation of multi-piperidine functionalized ion exchange membrane: dissolving the aryl ether-free polymer QPPAPi-x synthesized in the step (2) in DMSO, transferring the solution into a film-casting glass plate after the solution is dissolved, 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 a sodium chloride solution for 24 hours at room temperature to perform sufficient ion exchange;
the addition ratio of QPPAPi-x to DMSO is 0.10-0.15g.
Furthermore, 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 advantages that through condensation and quaternization reactions, the polyamine functionalized anion exchange membrane applied to the neutral flow battery is designed and prepared. The introduction of a plurality of quaternary amines can effectively improve the ion conductivity of the membrane, and the introduction of hydrophilic amino groups can assist in forming a good microphase separation channel, so that the membrane has higher ion conductivity. The multi-ammonium functionalized anion exchange membrane prepared by the method can show excellent battery performance, the energy efficiency of the multi-ammonium functionalized anion exchange membrane is far superior to that of common membranes such as AMVN and the like, the multi-ammonium functionalized anion exchange membrane has good stability, and the efficiency of the battery is not obviously attenuated after the battery is cycled for 1000 circles.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum: (a) a PPApi-x polymer; (b) QPPApi-x polymer; (c) FTIR spectrum of QPPAPi-x film.
Figure 2 is a graph of performance of three example membrane cells at different densities: (a) CE, (b) VE and (c) EE.
FIG. 3 is 40mA/cm 2 Cell cycle test plots for the membrane of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1 (x = 0.5)
(1) Synthesis of aryl ether-free polymers: weighing 0.43g of p-terphenyl, 0.35g of benzhydrylamine and 0.47g of 1-methyl-4-piperidone, transferring the p-terphenyl, the benzhydrylamine and the 1-methyl-4-piperidone into 3mL of dichloromethane, adding 0.45mL of trifluoroacetic acid and 3mL of trifluoromethanesulfonic acid in an ice bath, reacting for 4-5h in an ice bath condition to obtain viscous liquid, slowly pouring the liquid into anhydrous methanol to obtain a white fibrous polymer, carrying out suction filtration and washing with water for 24h, drying in an oven at 60 ℃ for 48h, and carrying out nuclear magnetic spectrum analysis on the polymer as shown in figure 1 (a).
(2) Quaternization of polypiperidine functionalized polymers: 0.25g of the polymer obtained in step (1) was added to 5mL of DMSO to dissolve it to form a clear solution, and 0.543g of 6-piperidine and 0.509g of potassium carbonate were added to react at 50 ℃ for 15 hours. After the reaction is finished, pouring the solution into ethyl acetate to precipitate, performing suction filtration and water washing, and drying at 60 ℃ for 48 hours, wherein the nuclear magnetic spectrum of the functionalized polymer is shown in figure 1 (b), and the infrared spectrum is shown in figure 1 (c).
(3) Preparation of multi-piperidine functionalized anion exchange membrane: taking 0.14g of the polymer synthesized in the step (2), dissolving the polymer in 5mL of DMSO, pouring the polymer into a glass plate with the size of 5cm multiplied by 5cm after the dissolution is finished, and placing the glass plate in an oven for film casting to obtain a film after the film casting is finished. The membrane was immersed in sodium chloride solution for 24h at room temperature for sufficient ion exchange.
Tests show that the ion conductivity of the polyammonium functionalized polymer anion exchange membrane prepared in the example is 19.4mS cm at 25 DEG C -1 The saline absorption rate was 39.6%, and the swelling degree was 16.8%. In a neutral flow battery, 40mA cm -2 At the time of electrical density, CE was 97.52% (as shown in FIG. 2 (a)), and EE was 88.40% (as shown in FIG. 2 (c)); the film prepared in this example was measured at 40mA/cm 2 The cell cycle test was performed 1000 timesThe battery performance did not change significantly after charging and discharging, as shown in fig. 3.
Example 2 (x = 0.4)
(1) Synthesis of aryl ether-free polymers: weighing 0.52g of p-terphenyl, 0.27g of diphenylmethylamine and 0.47g of 1-methyl-4-piperidone, transferring the p-terphenyl, the diphenylmethylamine and the 1-methyl-4-piperidone into 3mL of dichloromethane, adding 0.45mL of trifluoroacetic acid and 3mL of trifluoromethanesulfonic acid in an ice bath, reacting for 4-5h under an ice bath condition to obtain viscous liquid, slowly pouring the liquid into anhydrous methanol to obtain a white fibrous polymer, performing suction filtration and water washing for 24h, and drying in an oven at 60 ℃ for 48h.
(2) Quaternization of polypiperidine functionalized polymers: 0.25g of the polymer obtained in step (1) was added to 5mL of DMSO to dissolve it to form a clear solution, and 0.551g of 6-piperidine and 0.516g of potassium carbonate were added thereto to react at 50 ℃ for 15 hours. After the reaction was completed, the solution was poured into ethyl acetate to precipitate, filtered with suction and washed with water, and dried at 60 ℃ for 48 hours.
(3) Preparation of multi-piperidine functionalized anion exchange membrane: and (3) taking 0.14g of the polymer synthesized in the step (2), dissolving the polymer in 5mL of DMSO, pouring the polymer into a glass plate of 5cm multiplied by 5cm after the polymer is dissolved, and placing the glass plate in an oven for casting a membrane to obtain the membrane. The membrane was immersed in sodium chloride solution for 24h at room temperature for adequate ion exchange.
Tests show that the ion conductivity of the polyamine functionalized polymer anion exchange membrane prepared in the embodiment at 25 ℃ is 15.45mS cm -1 The saline absorption rate was 38.40%, and the swelling degree was 23.40%. In a neutral flow battery, 40mA cm -2 At the time of electrical density, 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 polymers: weighing 0.61g of p-terphenyl, 0.21g of diphenylmethylamine and 0.47g of 1-methyl-4-piperidone, transferring the p-terphenyl, the diphenylmethylamine and the 1-methyl-4-piperidone into 3mL of dichloromethane, adding 0.45mL of trifluoroacetic acid and 3mL of trifluoromethanesulfonic acid in an ice bath, reacting for 4-5h under an ice bath condition to obtain viscous liquid, slowly pouring the liquid into anhydrous methanol to obtain a white fibrous polymer, performing suction filtration and water washing for 24h, and drying in an oven at 60 ℃ for 48h.
(2) Quaternization of polypiperidine functionalized polymers: 0.25g of the polymer obtained in step (1) was added to 5mL of DMSO to dissolve the polymer and form a clear solution, and 0.559g of 6-piperidine and 0.523g of potassium carbonate were added thereto to conduct a reaction at 50 ℃ for 15 hours. After the reaction was completed, the solution was poured into ethyl acetate to precipitate, filtered with suction and washed with water, and dried at 60 ℃ for 48 hours.
(3) Preparation of multi-piperidine functionalized anion exchange membrane: and (3) taking 0.14g of the polymer synthesized in the step (2), dissolving the polymer in 5mL of DMSO, pouring the polymer into a glass plate of 5cm multiplied by 5cm after the polymer is dissolved, and placing the glass plate in an oven for casting a membrane to obtain the membrane. The membrane was immersed in sodium chloride solution for 24h at room temperature for adequate ion exchange.
Tests show that the ion conductivity of the polyamine functionalized polymer anion exchange membrane prepared in the embodiment at 25 ℃ is 12.24mS cm -1 The saline absorption rate was 36.96%, and the swelling degree was 15.40%. In a neutral flow battery, 40mA cm -2 When the density was high, 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 polymers: weighing 0.34g of p-terphenyl, 0.41g of diphenylmethylamine and 0.47g of 1-methyl-4-piperidone, transferring the p-terphenyl, the diphenylmethylamine and the 1-methyl-4-piperidone into 3mL of dichloromethane, adding 0.45mL of trifluoroacetic acid and 3mL of trifluoromethanesulfonic acid in an ice bath, reacting for 4-5h under an ice bath condition to obtain a relatively viscous liquid, slowly pouring the liquid into anhydrous methanol to obtain a white powdery polymer, performing suction filtration and washing for 24h, and drying for 48h in an oven at 60 ℃.
(2) Quaternization of polypiperidine functionalized polymers: 0.25g of the polymer obtained in step (1) was added to 5mL of DMSO to dissolve the polymer in the DMSO to obtain a transparent solution, and then 0.565g 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, filtered with suction and washed with water, and dried at 60 ℃ for 48 hours.
(3) Preparation of multi-piperidine functionalized anion exchange membrane: taking 0.14g of the polymer synthesized in the step (2), dissolving the polymer in 5mL of DMSO, pouring the polymer into a glass plate with the size of 5cm multiplied by 5cm after the dissolution is finished, and placing the glass plate in an oven for film casting to obtain a film after the film casting is finished. The membrane was immersed in sodium chloride solution for 24h at room temperature for adequate ion exchange.
Tests show that the ion conductivity of the polyamine-functionalized polymer anion exchange membrane prepared in the embodiment is 12.10mS cm at 25 DEG C -1 The film is equivalent to example 1, the salt absorption rate is 45.20%, the swelling degree is 25.40%, and the excessive swelling degree reduces the mechanical properties of the film and limits the practical use of the film. The content of the benzhydrylamine is continuously increased, so that the excessive water absorption and swelling of the membrane can be caused, and the use of the membrane is limited.
Example 5 (x = 0)
(1) Synthesis of aryl ether-free polymers: weighing 0.68g of p-terphenyl and 0.47g of 1-methyl-4-piperidone, transferring the p-terphenyl and the 1-methyl-4-piperidone into 3mL of dichloromethane, adding 0.45mL of trifluoroacetic acid and 3mL of trifluoromethanesulfonic acid in an ice bath, reacting for 4-5h under an ice bath condition to obtain a relatively viscous liquid, slowly pouring the liquid into anhydrous methanol to obtain a white powdery polymer, performing suction filtration, washing for 24h with water, and drying for 48h in an oven at 60 ℃.
(2) Quaternization of polypiperidine functionalized polymers: 0.25g of the polymer obtained in step (1) was added to 5mL of DMSO to dissolve the polymer in the DMSO to form a transparent solution, and then 0.562g 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, which was filtered off with suction and washed with water, and dried at 60 ℃ for 48 hours.
(3) Preparation of multi-piperidine functionalized anion exchange membrane: and (3) taking 0.14g of the polymer synthesized in the step (2), dissolving the polymer in 5mL of DMSO, pouring the polymer into a glass plate of 5cm multiplied by 5cm after the polymer is dissolved, and placing the glass plate in an oven for casting a membrane to obtain the membrane. The membrane was immersed in sodium chloride solution for 24h at room temperature for sufficient ion exchange.
Tests show that the ion conductivity of the polyamine-functionalized polymer anion exchange membrane prepared in the embodiment is 9.25mS cm at 25 DEG C -1 Lower than examples 1 to 3, the salt water absorption rate was 34.20% and the swelling degree was 12%, and thus it was confirmed that the presence of hydrophilic amine groups increased the salt water absorption rate of the membrane, thereby improving the conductivity of the membrane.
Claims (4)
1. A multi-piperidine functionalized anion exchange membrane characterized by the structural formula:
wherein: 0< -x < -1.
2. A preparation method of a multi-piperidine functionalized anion exchange membrane is characterized by comprising the following preparation 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 ℃, and reacting at 0-5 ℃ for 4-5h to obtain viscous liquid; slowly pouring the liquid into anhydrous methanol to obtain a white fibrous polymer, carrying out suction filtration, washing with water for 24 hours, and drying in an oven at 60 ℃ for 48 hours;
the mol ratio of the p-terphenyl to the benzhydrylamine to the 1-methyl-4-piperidone is 9-1 to 10;
the molar ratio of the 1-methyl-4-piperidone to the trifluoroacetic acid is 0.7;
the molar ratio of the 1-methyl-4-piperidone to the trifluoromethanesulfonic acid is 1;
the ratio of the 1-methyl-4-piperidone to the dichloromethane is 4.11mmol, namely 3mL;
(2) Quaternization of aryl ether-free polymer QPPAPi-x: taking the polymer PPPii-x obtained in the step (1), heating and dissolving the polymer PPPii-x 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 for precipitation, carrying out suction filtration and washing with water, and drying at 60 ℃ for 48 hours;
the molar ratio of the PPPix to the 6-piperidine ionic liquid is 1;
the molar ratio of PPPii-x to potassium carbonate is 1;
the adding ratio of the PPPi-x to the DMSO is 1g;
(3) Preparation of multi-piperidine functionalized ion exchange membrane: dissolving the aryl ether-free polymer QPPAPi-x synthesized in the step (2) in DMSO, transferring the solution into a film-casting glass plate after the solution is dissolved, 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 24h to perform sufficient ion exchange;
the addition ratio of QPPAPi-x to DMSO is 0.10-0.15g.
3. The method according to claim 2, wherein the drying temperature for the film formed by the casting method is 60 to 80 ℃ for 48 hours.
4. The method according to claim 2, wherein the reaction temperature in the step (2) is 50 ℃.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3970534A (en) * | 1974-01-11 | 1976-07-20 | Maruzen Oil Co. Ltd. | Graft copolymer and process for preparation thereof |
| US4965405A (en) * | 1988-02-29 | 1990-10-23 | Chugai Seiyaku Kabushiki Kaisha | Benzhydrylamine derivatives |
| US5863651A (en) * | 1989-09-01 | 1999-01-26 | The University Of Akron | Poly-pyridinium salts |
| KR20110010008A (en) * | 2009-07-23 | 2011-01-31 | 코오롱인더스트리 주식회사 | Manufacturing method of a novel polymer, a novel polymer manufactured by thereof and film manufactured using said polymer |
| US20130292252A1 (en) * | 2010-12-12 | 2013-11-07 | Ben-Gurion University Of The Negev Research And Development Authority | Anion exchange membranes, methods of preparation and uses |
| KR20170069029A (en) * | 2015-12-10 | 2017-06-20 | 한남대학교 산학협력단 | Anion exchange membrane for redox flow battery and method for preparing the same |
| CN111244518A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Water system neutral organic flow battery |
| US20210061966A1 (en) * | 2019-09-04 | 2021-03-04 | Research & Business Foundation Sungkyunkwan University | Anion exchange membrane based on aromatic polymer functionalized with imidazolium group, preparation method thereof, and vanadium redox flow battery including the membrane |
| US20210087387A1 (en) * | 2019-09-23 | 2021-03-25 | National Technology & Engineering Solutions Of Sandia, Llc | Poly(phenylene) with High Ion Selectivity for Use in Anion Exchange Membranes |
| CN112675927A (en) * | 2020-11-24 | 2021-04-20 | 大连理工大学 | Novel polypiperazinium functionalized anion exchange membrane and preparation method thereof |
| KR20210051350A (en) * | 2019-10-30 | 2021-05-10 | 상명대학교 천안산학협력단 | High stability pore-filled ion-exchange membranes for redox flow battery and method for preparing the same |
| CN113471497A (en) * | 2021-07-12 | 2021-10-01 | 大连理工大学 | Piperidine anion exchange membrane and preparation method thereof |
| CN113801300A (en) * | 2021-09-30 | 2021-12-17 | 惠州市亿纬新能源研究院 | Anion exchange polymer, preparation method and application thereof |
| CN114808028A (en) * | 2022-05-26 | 2022-07-29 | 大连理工大学 | Comb-shaped polyarylidene indole anion exchange membrane for alkaline electrolytic cell and preparation method thereof |
| CN115010907A (en) * | 2022-06-14 | 2022-09-06 | 天津市大陆制氢设备有限公司 | Polyarylpiperidine type anion exchange membrane containing hydrophilic and hydrophobic double side chains and preparation method thereof |
-
2022
- 2022-10-28 CN CN202211331187.4A patent/CN115572464B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3970534A (en) * | 1974-01-11 | 1976-07-20 | Maruzen Oil Co. Ltd. | Graft copolymer and process for preparation thereof |
| US4965405A (en) * | 1988-02-29 | 1990-10-23 | Chugai Seiyaku Kabushiki Kaisha | Benzhydrylamine derivatives |
| US5863651A (en) * | 1989-09-01 | 1999-01-26 | The University Of Akron | Poly-pyridinium salts |
| KR20110010008A (en) * | 2009-07-23 | 2011-01-31 | 코오롱인더스트리 주식회사 | Manufacturing method of a novel polymer, a novel polymer manufactured by thereof and film manufactured using said polymer |
| US20130292252A1 (en) * | 2010-12-12 | 2013-11-07 | Ben-Gurion University Of The Negev Research And Development Authority | Anion exchange membranes, methods of preparation and uses |
| KR20170069029A (en) * | 2015-12-10 | 2017-06-20 | 한남대학교 산학협력단 | Anion exchange membrane for redox flow battery and method for preparing the same |
| CN111244518A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Water system neutral organic flow battery |
| US20210061966A1 (en) * | 2019-09-04 | 2021-03-04 | Research & Business Foundation Sungkyunkwan University | Anion exchange membrane based on aromatic polymer functionalized with imidazolium group, preparation method thereof, and vanadium redox flow battery including the membrane |
| US20210087387A1 (en) * | 2019-09-23 | 2021-03-25 | National Technology & Engineering Solutions Of Sandia, Llc | Poly(phenylene) with High Ion Selectivity for Use in Anion Exchange Membranes |
| KR20210051350A (en) * | 2019-10-30 | 2021-05-10 | 상명대학교 천안산학협력단 | High stability pore-filled ion-exchange membranes for redox flow battery and method for preparing the same |
| CN112675927A (en) * | 2020-11-24 | 2021-04-20 | 大连理工大学 | Novel polypiperazinium functionalized anion exchange membrane and preparation method thereof |
| CN113471497A (en) * | 2021-07-12 | 2021-10-01 | 大连理工大学 | Piperidine anion exchange membrane and preparation method thereof |
| CN113801300A (en) * | 2021-09-30 | 2021-12-17 | 惠州市亿纬新能源研究院 | Anion exchange polymer, preparation method and application thereof |
| CN114808028A (en) * | 2022-05-26 | 2022-07-29 | 大连理工大学 | Comb-shaped polyarylidene indole anion exchange membrane for alkaline electrolytic cell and preparation method thereof |
| CN115010907A (en) * | 2022-06-14 | 2022-09-06 | 天津市大陆制氢设备有限公司 | Polyarylpiperidine type anion exchange membrane containing hydrophilic and hydrophobic double side chains and preparation method thereof |
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