CN115678073B - Branched poly (aryl piperidinium) anion exchange membrane and preparation method and application thereof - Google Patents
Branched poly (aryl piperidinium) anion exchange membrane and preparation method and application thereof Download PDFInfo
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 72
- -1 poly (aryl piperidinium Chemical compound 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000000446 fuel Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 16
- 238000005342 ion exchange Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 6
- 229920005594 polymer fiber Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000013557 residual solvent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005349 anion exchange Methods 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- 238000005985 Hofmann elimination reaction Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a branched poly (aryl piperidinium) anion exchange membrane and a preparation method and application thereof, and belongs to the technical field of membranes. The invention prepares a novel branched alkaline anion exchange membrane after ionization by a simple two-step synthesis method. The branched structure of the polymer produces high rigidity, and the water absorption and expansion ratio of the anion exchange membrane are greatly reduced, so that the dimensional stability is improved. The high OH-conductivity, the alkaline stability and the high mechanical strength of the branched poly (aryl piperidinium) anion exchange membrane disclosed by the invention can be used as an anion exchange membrane material for alkaline fuel cells.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a branched poly (aryl piperidinium) anion exchange membrane, and a preparation method and application thereof.
Background
The polymer electrolyte membrane fuel cell is an important new energy cell and has the advantages of environmental protection, high specific power, high reliability, low working temperature, high starting speed and the like. Polymer electrolyte membrane fuel cells include proton exchange membrane fuel cells and hydroxide ion exchange membrane fuel cells. Compared with a proton exchange membrane fuel cell, the hydroxide ion exchange membrane fuel cell has the advantages that the working environment is alkaline, the catalytic activity of the electrode is greatly improved, therefore, non-noble metal can be selected as a catalyst, the catalyst is more stable, the problems of cost and stability of the catalyst are expected to be solved, and the large-scale industrialization of the polymer electrolyte membrane fuel cell is realized.
Anion exchange membranes are a key component of alkaline fuel cells, and it is important to prepare Gao Qingyang anion exchange membranes that are stable in conductivity and chemical properties, thereby achieving high power density and long-term durability of the anion exchange membrane fuel cells. Various polymer backbones functionalized with cationic groups are used as anion exchange membrane materials, such as polyolefins, polystyrenes, and aromatic polymers, including polyphenylene oxides, polyarylethers, polyphenylene oxides, and polyethersulfones. Although the ion conductivity of Anion Exchange Membranes (AEMs) has increased significantly in recent years, the ion conductivity of AEMs is much lower than the current state-of-the-art proton exchange membranes (e.g., nafion) due to the lower mobility of hydroxide ions. The ionic conductivity of the AEMs can be improved to a certain extent by adding more cationic groups to the polymer main chain, but too many hydrophilic functional groups can in turn cause too high water absorption of the AEMs, excessive swelling and poor mechanical properties. Another approach to improve the conductivity of the AEMs is to build ion high-speed transport channels on the membrane. Microphase separation morphology can be induced by designing with block, comb/graft or ion aggregation structures to promote ionic conduction in the AEMs. On the other hand, the functional organic cations in the AEMs have strong nucleophilic and alkaline working conditions, and can undergo repeated degradation reactions such as Hofmann elimination, SN2 nucleophilic substitution or ylide and the like at high temperature, so that the ionic conductivity is reduced, and therefore, the large-scale industrialization of the alkaline fuel cell cannot be satisfied.
Disclosure of Invention
In a first aspect, the present invention provides a branched poly (arylpiperidinium) anion exchange membrane, characterized in that the branched poly (arylpiperidinium) anion exchange membrane comprises a branched poly (arylpiperidinium) polymer (b-PTP-x) having the structure of formula i:
wherein, -G-is an aromatic group, x is the mole percent of tetraphenylporphyrin to G, and x = 1-5.
Further, the G is selected from the following structures:
wherein n=1-4.
In a second aspect, the present invention provides a process for preparing the branched poly (arylpiperidinium) anion exchange membrane, the process comprising the steps of:
(1) Synthesis of branched Poly (arylpiperidine) Polymer (b-PTPA-x): adding G, tetraphenylporphyrin and N-methyl-4-piperidone into an organic solvent A, stirring at 0-25 ℃ for 15-45min, then dripping trifluoroacetic acid (TFA) and trifluoromethanesulfonic acid (TFSA) into the solution, reacting for 5-10 h, pouring the obtained viscous solution into an excessive solvent B, cutting precipitated polymer fibers into small blocks, filtering, and then using 1-3M K 2 CO 3 Washing overnight at 30-60 ℃, then washing with deionized water for three times, and drying in a vacuum oven at 50-90 ℃ for 10-24 hours to obtain a branched poly (aryl piperidine) polymer (b-PTPA-x), the structure of which is shown as formula II:
wherein, -G-is an aromatic group, x is the mole percent of tetraphenylporphyrin to G, and x = 1-5;
(2) Synthesis of branched Poly (triphenylpiperidinium) Polymer (b-PTP-x): suspending b-PTPA-x in organic solvent C, stirring at room temperature for 15-45min, and adding K 2 CO 3 And methyl iodide, stirring and reacting for 10-24 hours at room temperature in a dark place, adding an organic solvent D into the obtained viscous solution, filtering the precipitate, washing the precipitate with water for 3 times, and drying the precipitate in a vacuum oven at 50-90 ℃ for 10-24 hours to obtain branched poly (triphenylpiperidinium) (b-PTP-x);
(3) Preparation of branched poly (arylpiperidinium) anion exchange membranes: dissolving b-PTP-x in organic solvent C to obtain polymer solution, filtering the polymer solution by using 0.3-0.5 um Polytetrafluoroethylene (PTFE) filter, casting on glass plate, then evaporating at 50-90 deg.C for 10-24 hr, and evaporating at 100-120 deg.C for 10-to-one24h, vacuum drying at 100-120 ℃ for 10-24 h, thoroughly removing residual solvent, peeling the I-type film from the glass plate, performing ion exchange in 1-3M KBr solution at 50-90 ℃ for 10-24 h to obtain Br-type film, washing with deionized water for 3 times, removing residual salt, performing ion exchange in 1-3M KOH solution at 50-90 ℃ for 10-24 h to obtain OH-type film, and then performing ion exchange in N 2 Washing 3 times with de-aerated deionized water under an atmosphere to obtain the branched poly (arylpiperidinium) anion exchange membrane.
Further, in the step (1), the organic solvent a is selected from at least one of tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, or 1, 2-tetrachloroethane.
Further, in the step (1), the solvent B is at least one selected from water, methanol, absolute ethanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-pentanol, ethylene glycol and glycerol.
Further, in the step (1), the feeding amount ratio of the G, tetraphenylporphyrin and N-methyl-4-piperidone is 95-99:1-5:100.5-102.5.
Further, in step (1), the molar ratio of the trifluoroacetic acid (TFA) to the trifluoromethanesulfonic acid (TFSA) is from 1.0 to 1.2:10.0-10.1.
Further, in the step (2), the organic solvent C is selected from N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide or sulfolane.
Further, in the step (2), the organic solvent D is at least one selected from ethyl acetate, tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, and 1, 2-tetrachloroethane.
Further, in step (3), the branched poly (arylpiperidinium) anion exchange membrane is stored in the form of OH-in nitrogen to avoid CO 2 Is not limited, and the formation of carbonates.
In a third aspect, the present invention provides the use of the branched poly (arylpiperidinium) anion exchange membrane in the preparation of an alkaline fuel cell.
Further, in the fuel cell, the branched poly (arylpiperidinium) anion exchange membrane has an OH-conductivity of at least 120mS cm at 80 DEG C -1 。
The invention has the beneficial effects that:
the invention prepares a novel branched alkaline anion exchange membrane by synthesizing a branched polymer and ionizing the material by a simple two-step synthesis method. The branched structure of the polymer produces high rigidity, and the water absorption and expansion ratio of the anion exchange membrane are greatly reduced, so that the dimensional stability is improved. The high OH-conductivity, the alkaline stability and the high mechanical strength of the branched poly (aryl piperidinium) anion exchange membrane obtained by the invention can be used as an anion exchange membrane material for alkaline fuel cells.
The branched poly (arylpiperidinium) anion exchange membranes of the present invention are optimized for high OH-conductivity (OH-conductivity > 120mS cm at 80 ℃ C.) -1 ) High mechanical strength (tensile strength)>50MPa, elongation at break>30%) and dimensional stability, good processability, and excellent alkaline stability in 1M KOH at 80 ℃and>1000h)。
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to the drawings.
The following are various exemplary embodiments of the invention and should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to. The synthesis method used in the invention is a conventional synthesis method in the field, and the composition structure of the product can be estimated by using the raw materials.
The test methods used in the following examples:
performance test:
the device and the testing method related to the embodiment comprise the following steps:
ion Exchange Capacity (IEC) test method: three films containing branched poly (arylpiperidinium) polymer were taken, each 0.l g, immersed in 100mL, L mol/L NaCl solution for 24h, respectively, and immersed in 500mL deionized water for 24h, respectively, to wash away NaCl remaining on the surface. Drying in a vacuum oven at 75 ℃, weighing mass records respectively, and then soaking in 25mL of 0.2M NaNO respectively 3 The solution was stirred for 24h. Finally, adding an indicator potassium chromate solution into the solution, and using 0.1M AgNO 3 The solution was titrated and when a brick red precipitate appeared and did not change colour at 30 seconds, this was representative of the completion of the titration. Recording of consumed AgNO 3 Volume of solution. AgNO is to be carried out 3 The product of the concentration and the volume of the solution is divided by the mass of the dried film, i.e. IEC.
Conductivity test: the electrochemical workstation is produced by Shanghai Chen Hua instrument company and is CH1660C. The crosslinked films were tested for conductivity at different temperatures using alternating current impedance (EIS). The ionic resistance of the composite membrane was measured using a Solarton S1 1260&1287 electrochemical test system with a measured potential amplitude of 10mV and a test frequency range of 1 mhz-100 Hz. To reduce the error in the measurement caused by contact resistance, the resistance tested was the transverse (in-plane) resistance of the film sample. In the experiment, the composite film was cut to a size of 40mm×10mm, placed in a jig as shown in the figure, and the jig was placed in a vacuum oven and kept at 25 ℃ for 1 hour. The test temperature is from 30 ℃ to 80 ℃, and the composite film resistance is tested every 10 ℃. Then heating and maintaining for more than 2 hours, and reducing errors caused by temperature. Finally, calculating the ion conductivity sigma of the sample according to a formula: in the formula σ=l/(wdR), l is the length (cm) of the inter-electrode film, w is the width (cm) of the film, d is the thickness (μm) of the film, and R is the measured film resistance (mΩ).
Oxidation resistance test: the membrane was immersed in 80℃Fenton's reagent (3 wt% H 2 O 2 Ten 4ppm Fe 2+ ) And taking out the film after 12 hours, washing with deionized water, drying, weighing, and calculating the mass retention rate x of the film, namely the oxidation resistance of the film.
x＝m 1 M, where m is the initial mass of the dry film, m 1 Is the residual mass after soaking.
Fuel cell performance test: the used instrument is manufactured by the company scribner Associates co. in the United states, the model of the instrument is 850e multi-range fuel cell testing system, and the instrument is tested in a current mode. Test condition is H 2 And O 2 Completely moisturize, test temperature 60 ℃,80 ℃, H 2 And O 2 The flow rate was 200mL min-1.
Tensile strength test: wet film samples were tested 5 x 0.5cm using an instron 3300 electronic universal tester at a draw rate of 5mm/min.
Alkaline stability test: the prepared anion membranes are respectively soaked in deionized water at 60 ℃ and NaOH solution at room temperature, meanwhile, the conductivity of the anion membranes is measured, and the chemical change of the anion membranes is analyzed through the change of the conductivity of electrolyte membranes.
Example 1
Preparation of branched poly (arylpiperidinium) b-PTP-1 anion exchange Membrane:
(1) Synthesis of branched Poly (arylpiperidine) Polymer (b-PTPA-1): in a flask, biphenyl (2.28 g,0.99 eq), tetraphenylporphyrin (Por) (0.09 g,0.01 eq) and N-methyl-4-piperidone (1.70 g,1.005 eq) were added to the organic solvent DCM (17 mL). Stirring with an overhead stirrer at 0deg.C for 30min, then trifluoroacetic acid (TFA) (1.22 mL,1.1 eq.) and triFluoromethanesulfonic acid (TFSA) (13.3 ml,10.05 eq.) was added dropwise to the solution. After 6h of reaction, the viscous solution obtained was poured into excess methanol and the precipitated polymer fibers were cut into small pieces. After filtration, use 1M K 2 CO 3 Washing overnight at 50℃and then three times with deionized water, and drying in a vacuum oven at 80℃for 24h gave b-PTPA-1.
(2) Synthesis of branched Poly (arylpiperidinium) Polymer (b-PTP-1): b-PTPA-1 (1 g) was suspended in DMSO (30 mL). Stirring was carried out at room temperature for 30min. Subsequently, K is added 2 CO 3 (0.39 g) and methyl iodide (1 ml) were reacted at room temperature in the dark with stirring for 24 hours. To the viscous solution obtained was added ethyl acetate. The precipitate was filtered, washed 3 times with water and dried in a vacuum oven at 80℃for 24h to give b-PTP-1.
(3) Membrane preparation and ion exchange: preparation of branched poly (arylpiperidinium) anion exchange membranes: the b-PTP-1 (1 g) was dissolved in 30mL of DMSO, and the polymer solution was filtered through a 0.45um Polytetrafluoroethylene (PTFE) filter and cast onto a clean glass plate. Then evaporating at 80 ℃ for 12 hours, evaporating at 120 ℃ for 24 hours, and drying at 120 ℃ in vacuum for 24 hours, so as to thoroughly remove the residual solvent. The type I film peels off the glass plate. Ion exchange is carried out in 1M KBr solution for 12 hours at 80 ℃ to obtain a Br-type membrane, and the Br-type membrane is washed with deionized water for 3 times to remove residual salt. Ion-exchanging in 1M KOH solution at 80deg.C for 12 hr to obtain OH-type membrane, and then adding N 2 Washing 3 times with de-aerated deionized water under an atmosphere to obtain the branched poly (arylpiperidinium) anion exchange membrane. The membrane is stored in the form of OH-under nitrogen to avoid CO 2 Is not limited, and the formation of carbonates.
Performance test of branched poly (arylpiperidinium) b-PTP-1 anion exchange Membrane:
the test shows that the branched poly (arylpiperidinium) anion exchange membrane prepared in this example has an OH-conductivity of 123 mS.multidot.cm at 80 DEG C -1 Its anion exchange capacity is 1.36 mmol.g -1 The mass retention rate is 82%, the tensile strength is 52MPa, the elongation at break is 34%, and the alkaline stability is maintained for 1012 hours at 80 ℃ in 1M KOH, which shows that the homogeneous anion exchange membrane prepared in the embodiment has smaller swelling and has the following characteristicsSuitable ionic conductivity and anion exchange capacity, and good mechanical properties.
Example 2
Preparation of branched poly (arylpiperidinium) b-PTP-5 anion exchange Membrane:
(1) Synthesis of branched Poly (arylpiperidine) Polymer (b-PTPA-5): benzene (0.95 eq), tetraphenylporphyrin (Por) (0.05 eq) and N-methyl-4-piperidone (1.025 eq) were added to chloroform (20 mL) in a flask. Stirring was performed with an overhead stirrer at 25 ℃ for 45min, and then trifluoroacetic acid (TFA) (1.2 eq) and trifluoromethanesulfonic acid (TFSA) (10.1 eq) were added dropwise to the solution. After 10h of reaction, the viscous solution obtained was poured into an excess of absolute ethanol and the precipitated polymer fibers were cut into small pieces. After filtration, use 3M K 2 CO 3 Washing overnight at 60℃and then three times with deionized water, and drying in a vacuum oven at 90℃for 24h gave b-PTPA-5.
(2) Synthesis of branched Poly (arylpiperidinium) Polymer (b-PTP-5): b-PTPA-5 (3 g) was suspended in N-methylpyrrolidone (60 mL). Stirring was carried out at room temperature for 45min. Subsequently, K is added 2 CO 3 (0.4 g) and methyl iodide (3 ml) were stirred at room temperature in the dark for 24 hours. To the viscous solution obtained was added dichloromethane. The precipitate was filtered, washed 3 times with water and dried in a vacuum oven at 90℃for 24h to give b-PTP-5.
(3) Preparation of branched poly (arylpiperidinium) anion exchange membranes: b-PTP-5 (3 g) was dissolved in 60mL of methylene chloride, and the polymer solution was filtered through a 0.5um Polytetrafluoroethylene (PTFE) filter and cast onto a clean glass plate. Then evaporated at 90 ℃ for 24 hours, 120 ℃ for 24 hours, and dried at 120 ℃ in vacuum for 24 hours, the residual solvent is thoroughly removed. The type I film peels off the glass plate. Ion exchange is carried out in 3M KBr solution at 90 ℃ for 24 hours to obtain a Br-type membrane, and the Br-type membrane is washed with deionized water for 3 times to remove residual salt. Ion-exchanging in 3M KOH solution at 90deg.C for 24 hr to obtain OH-type membrane, and then adding N 2 Washing 3 times with de-aerated deionized water under an atmosphere to obtain the branched poly (arylpiperidinium) anion exchange membrane. The membrane is stored in the form of OH-under nitrogen to avoid CO 2 Is not limited, and the formation of carbonates.
Performance test of branched poly (arylpiperidinium) b-PTP-5 anion exchange Membrane:
the test shows that the branched poly (arylpiperidinium) anion exchange membrane prepared in this example has OH at 80 ℃ - Conductivity of 121 mS.cm -1 Its anion exchange capacity is 1.36 mmol.g -1 The mass retention rate is 82%, the tensile strength is 55MPa, the elongation at break is 36%, and the alkaline stability is kept for 1015h at 80 ℃ in 1M KOH, so that the homogeneous anion exchange membrane prepared in the embodiment has small swelling, proper ionic conductivity and anion exchange capacity and good mechanical property.
Example 3
Preparation of branched poly (arylpiperidinium) b-PTP-2 anion exchange Membrane:
(1) Synthesis of branched Poly (arylpiperidine) Polymer (b-PTPA-2): in a flask, terphenyl (0.98 eq), tetraphenylporphyrin (Por) (0.02 eq) and N-methyl-4-piperidone (1.02 eq) were added to 1, 2-tetrachloroethane (15 mL). At 0 ℃, stirring with an overhead stirrer for 15min, then trifluoroacetic acid (TFA) (1.0 eq) and trifluoromethanesulfonic acid (TFSA) (10.0 eq) were added dropwise to the solution. After 5h of reaction, the viscous solution obtained was poured into excess ethylene glycol and the precipitated polymer fibers were cut into small pieces. After filtration, 1MK was used 2 CO 3 Washing overnight at 30℃and then three times with deionized water, and drying in a vacuum oven at 50℃for 10h gave b-PTPA-2.
(2) Synthesis of branched Poly (arylpiperidinium) Polymer (b-PTP-2): b-PTPA-2 (1 g) was suspended in N, N-dimethylacetamide (30 mL). Stirring was carried out at room temperature for 15min. Subsequently, K is added 2 CO 3 (0.2 g) and methyl iodide (1 ml) were reacted at room temperature in the dark with stirring for 10 hours. 1, 2-tetrachloroethane was added to the viscous solution obtained. The precipitate was filtered, washed 3 times with water and dried in a vacuum oven at 50℃for 10h to give b-PTP-2.
(3) Preparation of branched poly (arylpiperidinium) anion exchange membranes: b-PTP-2 (1 g) was dissolved in 30mL of N, N-dimethylacetamide and the polymer solution was passed through a 0.3um Polytetrafluoroethylene (PTFE) filterFiltered and cast onto a clean glass plate. Then evaporating at 50 ℃ for 10 hours, evaporating at 100 ℃ for 10 hours, and drying at 100 ℃ for 10 hours in vacuum, so as to thoroughly remove the residual solvent. The type I film peels off the glass plate. Ion exchange is carried out in 1M KBr solution at 50 ℃ for 10 hours to obtain a Br-type membrane, and the Br-type membrane is washed with deionized water for 3 times to remove residual salt. Ion-exchanging in 1M KOH solution at 50deg.C for 10 hr to obtain OH-type membrane, and then adding N 2 Washing 3 times with de-aerated deionized water under an atmosphere to obtain the branched poly (arylpiperidinium) anion exchange membrane. The membrane is stored in the form of OH-under nitrogen to avoid CO 2 Is not limited, and the formation of carbonates.
Performance test of branched poly (arylpiperidinium) b-PTP-2 anion exchange Membrane:
the test shows that the branched poly (arylpiperidinium) anion exchange membrane prepared in this example has an OH-conductivity of 125 mS.multidot.cm at 80 ℃ -1 Its anion exchange capacity is 1.36 mmol.g -1 The mass retention rate is 82%, the tensile strength is 57MPa, the elongation at break is 31%, and the alkaline stability is kept for 1018h at 80 ℃ and 1M KOH, which shows that the homogeneous anion exchange membrane prepared in the embodiment has smaller swelling, proper ionic conductivity and anion exchange capacity and good mechanical property.
Example 4
Preparation of branched poly (arylpiperidinium) b-PTP-3 anion exchange Membrane:
(1) Synthesis of branched Poly (arylpiperidine) Polymer (b-PTPA-3): in a flask, tetraphenyl (0.97 eq), tetraphenylporphyrin (Por) (0.03 eq) and N-methyl-4-piperidone (1.008 eq) were added to carbon tetrachloride (18 mL). Stirring was performed with an overhead stirrer at 10 ℃ for 25min, and then trifluoroacetic acid (TFA) (1.1 eq) and trifluoromethanesulfonic acid (TFSA) (10.05 eq) were added dropwise to the solution. After 8h of reaction, the viscous solution obtained was poured into excess isopropanol and the precipitated polymer fibers were cut into small pieces. After filtration, use 2K 2 CO 3 Washing overnight at 50℃and then three times with deionized water, and drying in a vacuum oven at 80℃for 12h gave b-PTPA-3.
(2) Branched Poly (arylpiperidinium) polymer (b-PTP-3)Is synthesized by the following steps: b-PTPA-3 (2 g) was suspended in N, N-dimethylacetamide (45 mL). Stirring was carried out at room temperature for 30min. Subsequently, K is added 2 CO 3 (0.3 g) and methyl iodide (2 ml) were stirred at room temperature in the dark for 12 hours. Dichloroethane was added to the viscous solution obtained. The precipitate was filtered, washed 3 times with water and dried in a vacuum oven at 80℃for 12h to give b-PTP-3.
(3) Preparation of branched poly (arylpiperidinium) anion exchange membranes: b-PTP-3 (2 g) was dissolved in 45mL of N, N-dimethylacetamide, and the polymer solution was filtered through a 0.4um Polytetrafluoroethylene (PTFE) filter and cast onto a clean glass plate. Then evaporating at 80 ℃ for 12 hours, evaporating at 110 ℃ for 12 hours, and vacuum drying at 110 ℃ for 12 hours to thoroughly remove the residual solvent. The type I film peels off the glass plate. Ion exchange is carried out in 2M KBr solution for 12h at 80 ℃ to obtain Br-type membrane, and the Br-type membrane is washed with deionized water for 3 times to remove residual salt. Ion-exchanging in 2M KOH solution at 80deg.C for 12 hr to obtain OH-type membrane, and then adding N 2 Washing 3 times with de-aerated deionized water under an atmosphere to obtain the branched poly (arylpiperidinium) anion exchange membrane. The membrane is stored in the form of OH-under nitrogen to avoid CO 2 Is not limited, and the formation of carbonates.
Performance test of branched poly (arylpiperidinium) b-PTP-3 anion exchange Membrane:
the test shows that the branched poly (arylpiperidinium) anion exchange membrane prepared in this example has an OH-conductivity of 129 mS.multidot.cm at 80 ℃ -1 Its anion exchange capacity is 1.36 mmol.g -1 The mass retention rate is 82%, the tensile strength is 56MPa, the elongation at break is 32%, and the alkaline stability is 1030h at 80 ℃ in 1M KOH, which shows that the homogeneous anion exchange membrane prepared in the embodiment has small swelling, proper ionic conductivity and anion exchange capacity and good mechanical property.
Example 5
Alkali resistance stability test: the branched poly (arylpiperidinium) anion exchange membrane obtained in example 2 was immersed in 1mol/LKOH, respectively at 60℃for 5d,7d, and then immersed in deionized water until neutral.
Tests show that the conductivity of the branched poly (aryl piperidinium) anion exchange membrane prepared in the embodiment is kept 89% and 78% after being soaked for 5d and 7d, and the homogeneous anion exchange membrane prepared in the embodiment has good alkali resistance stability.
Comparative example 1
Branched poly (arylpiperidinium) b-PTP-7 anion exchange membranes were prepared in the same manner as in example 1 except that the amounts of biphenyl (2.14 g,0.93 eq.) and tetraphenylporphyrin (Por) (0.63 g,0.07 eq.) were charged.
Tests have shown that the branched poly (arylpiperidinium) anion exchange membrane prepared in this comparative example has an OH-conductivity of 67mS cm at 80deg.C -1 Its anion exchange capacity is 0.79 mmol.g -1 The mass retention rate was 55%, the tensile strength was 42MPa, the elongation at break was 23%, and the alkaline stability was maintained at 80 ℃ and 1M KOH for 728h, and the results showed that the performance of the anion-exchange membrane prepared in this comparative example was significantly reduced compared to the homogeneous anion-exchange membrane prepared in example 1.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. A branched poly (arylpiperidinium) anion exchange membrane comprising a branched poly (arylpiperidinium) polymer (b-PTP-x) having the structure of formula i:
wherein, -G-is an aromatic group, x is the mole percent of tetraphenylporphyrin to G, and x = 1-5.
2. The branched poly (arylpiperidinium) anion exchange membrane of claim 1, wherein G is selected from the following structures:
wherein n=1-4.
3. A process for preparing a branched poly (arylpiperidinium) anion exchange membrane as described in claim 1 or 2, said process comprising the steps of:
(1) Synthesis of branched Poly (arylpiperidine) Polymer (b-PTPA-x): adding G, tetraphenylporphyrin and N-methyl-4-piperidone into an organic solvent A, stirring at 0-25 ℃ for 15-45min, then dripping trifluoroacetic acid (TFA) and trifluoromethanesulfonic acid (TFSA) into the solution, reacting for 5-10 h, pouring the obtained viscous solution into an excessive solvent B, cutting precipitated polymer fibers into small blocks, filtering, and then using 1-3M K 2 CO 3 Washing overnight at 30-60 ℃, then washing with deionized water for three times, and drying in a vacuum oven at 50-90 ℃ for 10-24 hours to obtain a branched poly (aryl piperidine) polymer (b-PTPA-x), the structure of which is shown as formula II:
wherein, -G-is an aromatic group, x is the mole percent of tetraphenylporphyrin to G, and x = 1-5;
(2) Synthesis of branched Poly (arylpiperidinium) Polymer (b-PTP-x): suspending b-PTPA-x in organic solvent C, stirring at room temperature for 15-45min, and adding K 2 CO 3 And methyl iodide, stirring and reacting for 10-24 hours at room temperature in a dark place, adding an organic solvent D into the obtained viscous solution, filtering the precipitate, washing the precipitate with water for 3 times, and drying the precipitate in a vacuum oven at 50-90 ℃ for 10-24 hours to obtain branched poly (aryl piperidinium) (b-PTP-x);
(3) Branched poly (aryl piperidines)Onium) anion exchange membrane preparation: dissolving b-PTP-x in organic solvent C to obtain polymer solution, filtering the polymer solution by a 0.3-0.5 um Polytetrafluoroethylene (PTFE) filter, casting on a glass plate, evaporating at 50-90 ℃ for 10-24 h, evaporating at 100-120 ℃ for 10-24 h, vacuum drying at 100-120 ℃ for 10-24 h, thoroughly removing residual solvent, peeling off the I-type film from the glass plate, ion-exchanging at 50-90 ℃ for 10-24 h in 1-3M KBr solution to obtain Br-type film, washing 3 times with deionized water, removing residual salt, ion-exchanging at 50-90 ℃ in 1-3M KOH solution for 10-24 h to obtain OH-type film, and then washing with N-type film 2 Washing 3 times with de-aerated deionized water under an atmosphere to obtain the branched poly (arylpiperidinium) anion exchange membrane.
4. The process according to claim 3, wherein in the step (1), the organic solvent A is at least one selected from tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, dichloroethane and 1, 2-tetrachloroethane.
5. The process according to claim 3, wherein in the step (1), the solvent B is at least one selected from the group consisting of water, methanol, absolute ethanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, ethylene glycol, and glycerol.
6. The method according to claim 3, wherein in the step (1), the ratio of the G, tetraphenylporphyrin and N-methyl-4-piperidone is 95 to 99:1-5:100.5-102.5.
7. A process according to claim 3, wherein in step (1), the molar ratio of trifluoroacetic acid (TFA) to trifluoromethanesulfonic acid (TFSA) is from 1.0 to 1.2:10.0-10.1.
8. A process according to claim 3, wherein in step (2), the organic solvent C is selected from the group consisting of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide and sulfolane; the organic solvent D is at least one selected from ethyl acetate, tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or 1, 2-tetrachloroethane.
9. Use of a branched poly (arylpiperidinium) anion exchange membrane according to claim 1 or 2 and a branched poly (arylpiperidinium) anion exchange membrane obtained according to the method of preparation of any of claims 3-8 for the preparation of alkaline fuel cells.
10. The use according to claim 9, wherein in the fuel cell the branched poly (arylpiperidinium) anion exchange membrane has an OH "conductivity of at least 120mS cm at 80 ℃ -1 。
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| CN110690487A (en) * | 2019-11-07 | 2020-01-14 | 大连理工大学 | Preparation method of basic anion membrane based on branched anaerobic main chain |
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| CN110690487A (en) * | 2019-11-07 | 2020-01-14 | 大连理工大学 | Preparation method of basic anion membrane based on branched anaerobic main chain |
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