CN112175217A - Anion exchange membrane containing arylene piperidine and diketone monomer copolymer and preparation method and application thereof - Google Patents
Anion exchange membrane containing arylene piperidine and diketone monomer copolymer and preparation method and application thereof Download PDFInfo
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- CN112175217A CN112175217A CN202010903752.4A CN202010903752A CN112175217A CN 112175217 A CN112175217 A CN 112175217A CN 202010903752 A CN202010903752 A CN 202010903752A CN 112175217 A CN112175217 A CN 112175217A
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- piperidine
- exchange membrane
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- 239000000178 monomer Substances 0.000 title claims abstract description 103
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 55
- -1 arylene piperidine Chemical compound 0.000 title claims abstract description 37
- 229920001577 copolymer Polymers 0.000 title claims abstract description 34
- 125000005594 diketone group Chemical group 0.000 title claims abstract description 34
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 69
- 229920000642 polymer Polymers 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 26
- 239000000446 fuel Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 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 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 125000003386 piperidinyl group Chemical group 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 229920006158 high molecular weight polymer Polymers 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract 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 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 19
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 description 18
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- 239000012528 membrane Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 10
- 229920000554 ionomer Polymers 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229920000412 polyarylene Polymers 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 239000003930 superacid Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000008378 aryl ethers Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BDVKAMAALQXGLM-UHFFFAOYSA-N 1-ethylpiperidin-4-one Chemical compound CCN1CCC(=O)CC1 BDVKAMAALQXGLM-UHFFFAOYSA-N 0.000 description 1
- PRRZDZJYSJLDBS-UHFFFAOYSA-N 3-bromo-2-oxopropanoic acid Chemical compound OC(=O)C(=O)CBr PRRZDZJYSJLDBS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- XGLLQDIWQRQROJ-UHFFFAOYSA-N methyl 3,3,3-trifluoro-2-oxopropanoate Chemical compound COC(=O)C(=O)C(F)(F)F XGLLQDIWQRQROJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000002047 photoemission electron microscopy Methods 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 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 description 1
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- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
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Abstract
The invention relates to an anion exchange membrane containing an arylene piperidine and diketone monomer copolymer, a preparation method and application thereof, belonging to the technical field of alkaline water electrolyzers. The invention provides a copolymer containing arylene piperidine and diketone monomers, wherein a main chain of the copolymer consists of high molecular weight ether bond-free, rigid and hydrophobic aryl skeletons, high alkali stability piperidine cations are combined, and high-reactivity monomer diketone is used for copolymerization with the high molecular weight piperidine cations to prepare a high molecular weight polymer with adjustable IEC, and the high alkalinity of the piperidine cations is reserved. The obtained anion exchange membrane of the copolymer of the poly-arylene piperidine and the diketone monomer simultaneously proves excellent chemical stability, film forming property, conductivity and mechanical strength.
Description
Technical Field
The invention belongs to the technical field of alkaline water electrolyzers, and relates to a porous polymer ion exchange membrane material, in particular to an anion exchange membrane containing an arylene piperidine and diketone monomer copolymer, and a preparation method and application thereof.
Background
With the increasing global demand for alternative energy sources, electrochemical energy storage and conversion technologies such as Fuel cells (Fuel cells), flow batteries, supercapacitors and water electrolysis have been recognized as the most viable and efficient technologies for portable, stationary and transportation applications. At the same time, Anion Exchange Membrane (AEM) technology has become an increasingly active area of research over the past decade due to its wide application in water electrolysis, redox flow batteries and Alkaline Anion Exchange Membrane Fuel Cells (AAEMFC). Many studies have been made on AAEMFCs, mainly because of their advantages in oxygen reduction kinetics, improved fuel conversion, and the use of non-precious catalysts. However, the development of AEM is hampered by its low ionic conductivity and chemical stability. Typically, in a generally dilute solution, H+Has ion mobility far greater than OH-The ionic conductivity of (a). Thus, AEM has lower ionic conductivity than proton exchange membranes. In the pursuit of high power density fuel cells and excellent performance alkaline electrolyzers, AEM requires higher ionic conductivity. In addition, the long-term stability of AEM can provide good mechanical properties and ionic conductivity, thus ensuring the application of high performance fuel cells and water electrolysis technologies. The chemical stability of AEM is mainly related to the basic stability of the polymer backbone and ionic groups. The problem to be solved is that the demand for high performance fuel cells and alkaline electrolysis water technology is hardly met by ordinary AEM.
Traditionally, some commercial polymers including polyphenylene oxide (PPO) and polyarylene ether ketone (PAEK) plasma exchange membranes have aryl ether linkages in their backbone chemical structure that are susceptible to OH-Or OH radicals, thereby exacerbating the degradation of the ion-exchange membrane (j. mater. chem. a,2018,6, 15456-. Therefore, the direction of AEM research has been shifted to polymers containing no ether linkage. The Miyatake group reported a series of polyphenylene alkylene-based anionically conducting polymers with reasonable base stability of 1000h in 1M KOH (Macromolecules,2018,51, 3394-3404). However, polyphenyleneThe preparation of the alkylidene group is very complicated and expensive. The Bae group used solvent processable poly (biphenylalkylenes) with high molecular weight as AEM, showing high base stability of 60d at 95 ℃ (J.Power Sources,2018,375, 367-372). The poly (biphenylalkylene) polymers can be prepared by superacid catalyzed polymerization of materials without aryl ether linkages. These polymers have excellent chemical and mechanical stability and are suitable for use in AEM backbones. In recent years, polyarylene piperidines prepared by superacid catalyzed polymerization have been used as AEM for alkaline fuel cells and show higher alkaline stability (Nature Energy,2019,4, 392-. Furthermore, the AEM based on polyarylene piperidines is at 80 ℃ and 1.5W/cm2The high power density alkaline fuel cell of (2) shows very high performance. Kim's research group reported a series of polyinosine biphenyl copolymers (PIB) prepared by super acid catalyzed polymerization for use as Proton Exchange Membranes (PEM). The series has high thermal stability and chemical stability (int. j. hydrogen Energy,2018,43, 11862-11871). Given their excellent performance as PEMs and the ease with which PIBs can be prepared and functionalized, they can also be used as AEMs. The Zhu research group at the university of general engineering will find that based on PIB as AEM, it shows good alkaline stability, oxidation durability, hydroxide ion conductivity and excellent fuel cell performance (j. mater. chem. a,2019,7, 6883-. Therefore, the AEM based on the PIB has positive development prospect in the anion exchange membrane fuel cell. The above materials still have a large gap from the commercialization requirements.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides an anion exchange membrane containing arylene piperidine and diketone monomer copolymer, which has higher hydroxide conductivity, excellent alkali stability and good mechanical property, and a preparation method and application thereof.
The design concept of the invention is as follows: the invention provides a copolymer containing arylene piperidine and diketone monomers, wherein a main chain of the copolymer consists of high molecular weight ether bond-free, rigid and hydrophobic aryl skeletons, high alkali stability piperidine cations are combined, and high-reactivity monomer diketone is used for copolymerization with the high molecular weight piperidine cations to prepare a high molecular weight polymer with adjustable IEC, and the high alkalinity of the piperidine cations is reserved. The obtained anion exchange membrane of the copolymer of the poly-arylene piperidine and the diketone monomer simultaneously proves excellent chemical stability, film forming property, conductivity and mechanical strength.
The invention is realized by the following technical scheme.
An anion exchange membrane comprising a copolymer of an arylene piperidine and a diketone monomer, comprising a copolymer of the following repeating structural units:
wherein Ar is a divalent organic group containing an aromatic ring, R1And R2Represent identical or different hydrocarbon radicals; x—Represents Br—、I—、Cl—、OH—、HCO3 —Or CO3 2-(ii) a n represents the degree of polymerization, n is a positive integer of 10-200, and the weight average molecular weight is 5000-800000; m is the mole percentage of the piperidine onium salt-containing part in the copolymer, and m is any number of 0-100.
An anion exchange membrane comprising a copolymer of an arylene piperidine and a diketone monomer, wherein:
ar is any one of the following groups:
containing R1，R2The radical piperidinium salt is any one of the following radicals:
containing R3，R4The carbonyl-containing matter of the group is any one of the following groups:
a preparation method of an anion exchange membrane containing arylene piperidine and diketone monomer copolymer comprises the following steps:
(1) firstly, dissolving aromatic hydrocarbon containing Ar groups in a dichloromethane solution at room temperature to prepare a transparent solution; then, adding a ketone monomer containing a piperidine ring and a diketone monomer into the dichloromethane solution, wherein the ketone monomer containing the piperidine ring and the diketone monomer are fully dissolved, the molar ratio of the ketone monomer containing the piperidine ring to the diketone monomer is 1:1-10, and the solid content is 10-20 wt%;
(2) dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in step (1) at 0 ℃, wherein the molar ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1:10.5, initiating polymerization at 0 ℃, and then reacting at room temperature for 2-24 h; after the polymerization reaction is finished, pouring the solution into methanol or ethanol to obtain a fibrous polymer, adding a potassium carbonate solution with the volume molar concentration of 1M after multiple times of precipitation and washing, and removing redundant acid in the solution; filtering, boiling the obtained fibrous solid polymer with water, filtering again, drying the obtained polymer in a vacuum drying oven at 60 ℃ for 24h, and weighing;
(3) and (3) dissolving the dried polymer in the step (2) in a polar solvent at 25-100 ℃, wherein the concentration of the polymer in the solution is 2-10 wt%, directly casting the obtained polymer solution on a glass plate or a stainless steel plate, flattening by using a casting knife, drying at 60-100 ℃ for 5-24h to form a film, and finally drying at 80-150 ℃ for 1-24h in vacuum to obtain the anion exchange membrane containing the arylene piperidine and diketone monomer copolymer.
Further, in the step (3), the polar solvent is one or more of NMP, DMF, DMAc, DMSO.
Further, in the step (3), the thickness of the prepared anion exchange membrane containing the copolymer of the arylene piperidine and the diketone monomer is 10-100 μm.
An anion exchange membrane containing arylene piperidine and diketone monomer copolymer is applied to an alkaline anion exchange membrane fuel cell or an alkaline anion exchange membrane water electrolysis device.
Use in alkaline electrolyte fuel cells:
1) procedure for manufacturing membrane/electrode assembly (MEA), Pt/C catalyst (40 wt%), deionized water, isopropyl alcohol and ionomer solution (AS-4, 5 wt%) were mixed uniformly using magnetic stirring and ultrasonic waves. Well-dispersed catalyst ink was sprayed onto both sides of the anion exchange membrane to form an anode and a cathode. The loading of the catalyst and ionomer were 0.5mg cm, respectively-2And 20 wt%. Sandwiching the catalyst-coated membrane between two sheets of carbon paper to prepare an MEA;
2) the effective area is 5cm2Is mounted in a single cell test system. Fuel cell performance was tested at 60 ℃ under fully humidified conditions without backpressure, H2And O2The flow rate of (2) is 200 sccm. After complete activation in constant voltage mode, the polarization curve was measured. Then 100mA cm was applied to the fuel cell-2The life durability test was performed and the cell voltage was recorded as a function of time.
The application in the alkaline anion exchange membrane water electrolysis device is as follows:
1) an MEA of an electrolytic water device was prepared, and an anode and a cathode were prepared by a Catalyst Coated Substrate (CCS) method. The anode was prepared as follows: IrO is to be mixed2The powder was mixed with deionized water and isopropanol and then the PTFE emulsion was added. After 30 minutes of sonication, the catalyst ink was stirred in a water bath at 85 ℃ and water and isopropanol were evaporated. The paste obtained was coated on a platinized porous Ti plate. An ionomer solution (5 wt% solids copolymer in ethanol) was also sprayed onto the surface of the catalyst layer, drying the ionomer and IrO2The loading amounts in the anode were 1.5 and 8 mg-cm, respectively-2. For the cathode preparation, Pt/C (40 wt%), deionized water, isopropanol, and PTFE emulsion (6 wt% in the cathode) were mixed, and the prepared ink was sonicated for 30 minutes and sprayed on carbon paper with a Pt loading of 0.4mg cm-2. The ionomer solution was also sprayed on the surface (1.5mg cm)-2). The electrode area is 8cm2. Finally, both electrodes and membrane were immersed in 1M NaOH for 24h for ion exchange and rinsed several times with deionized water before use;
2) the water electrolysis apparatus is assembled by sandwiching the membrane electrode between the cathode and the anode. A platinized porous Ti plate was used as a current collector in the cathode. Electrochemical tests were performed by soaking in anode and cathode deionized water, with the temperature maintained at 50 ℃. The polarization curve was obtained by measuring the cell voltage at different current densities and was measured at 50 ℃ and 200 mA-cm-2The durability thereof was evaluated at a constant current.
Further, the electrolyte in the alkaline water electrolysis device is one of potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate or pure water.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention discloses an anion exchange membrane containing arylene piperidine and diketone monomer copolymer with mild polymerization conditions, which is a copolymerization type polymer with excellent alkali stability and no ether bond on a framework and cationic piperidinium salt.
(2) The prepared polymer has good solubility and film-forming property, and can be dissolved in one or more polar solvents of NMP, DMF, DMAc and DMSO at room temperature;
(3) the obtained anion exchange membrane has good thermal stability and mechanical property, the decomposition temperature of the polymer can reach 400-600 ℃, and the tensile strength can reach 80-120 MPa;
(4) the anion exchange membrane is applied to an alkaline electrolyte fuel cell, and has excellent power density and service life;
(5) the anion exchange membrane is applied to alkaline electrolytic water at 500mA.cm2The temperature can reach 2.03V, and the temperature is 50 ℃, and the temperature is 200mA cm-2Continuously and stably operated at the constant current of (1) for more than 500 hours.
Drawings
FIG. 1 is the NMR spectrum of the polymer prepared in example III.
Fig. 2 is a polarization curve and a power density curve of the polymer membrane prepared in the first example under an alkaline electrolyte fuel cell.
FIG. 3 is a polarization curve of the polymer membrane prepared in example four at different temperatures on an alkaline electrolyzed water apparatus.
FIG. 4 is a stability test of the polymer membrane prepared in example four on an alkaline water electrolysis apparatus.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the examples follow conventional experimental conditions. In addition, it will be apparent to those skilled in the art that various modifications or improvements can be made to the material components and amounts in these embodiments without departing from the spirit and scope of the invention as defined in the appended claims.
Example one
A preparation method of an anion exchange membrane containing arylene piperidine and diketone monomer copolymer comprises the following steps:
(1) under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding isatin monomer and N-methyl-4-piperidone monomer, and dissolving the mixture in the solution in the same way, wherein the molar ratio of the two monomers is 1: 3, controlling the solid content to be 15 wt%;
(2) to the solution of step (1) was added dropwise trifluoromethanesulfonic acid (TFSA) and trifluoroacetic acid (TFA) at 0 ℃. The polymerization is initiated at-15-0 ℃ and then reacted at room temperature for 12 h. After the reaction is finished, pouring the solution into methanol or ethanol to obtain a fibrous polymer, adding 1M potassium carbonate solution to remove redundant acid in the solution after multiple times of precipitation and washing, filtering, boiling the obtained fibrous solid polymer with water, filtering, drying the obtained polymer for 24 hours at the temperature of 60 ℃ in a vacuum drying oven, and weighing; wherein the molar ratio of TFA to TFSA in the reaction system is 1: 10.5.
(3) the polymer is dissolved in a polar solvent at 25 ℃, methyl iodide is added, and reaction is carried out for 24 hours at 25 ℃. After the reaction is finished, ether is used for precipitation, drying and weighing are carried out after multiple times of washing, the obtained polymer solution is directly cast on a glass plate or a stainless steel plate, the glass plate or the stainless steel plate is pushed to be flat by a film casting knife, the glass plate or the stainless steel plate is dried for 5-24 hours at the temperature of 60-100 ℃ to form a film, then the film is dried for 5-24 hours in vacuum at the temperature of 80-150 ℃, and the thickness of the film is 10-100 mu m. The membrane was subjected to hydroxide ion exchange at 80 ℃ under 1M sodium hydroxide to obtain an anion exchange membrane.
The application of the anion exchange membrane comprises the following steps:
the resulting polymeric anion exchange membrane is used in an alkaline electrolyte fuel cell.
1) Procedure for manufacturing membrane/electrode assembly (MEA), Pt/C catalyst (40 wt%), deionized water, isopropyl alcohol and ionomer solution (AS-4, 5 wt%) were mixed uniformly using magnetic stirring and ultrasonic waves. Well-dispersed catalyst ink was sprayed onto both sides of the anion exchange membrane to form an anode and a cathode. The loading of the catalyst and ionomer were 0.5mg cm, respectively-2And 20 wt%. Sandwiching the catalyst-coated membrane between two sheets of carbon paper to prepare an MEA;
2) a Membrane Electrode Assembly (MEA) with an effective area of 5cm2 was installed in the single cell test system. Fuel cell performance was tested at 60 ℃ under fully humidified conditions without backpressure, H2And O2The flow rate of (2) is 200 sccm. After complete activation in constant voltage mode, the polarization curve was measured. Then 100mA cm was applied to the fuel cell-2The life durability test was performed and the cell voltage was recorded as a function of time.
The obtained polymer anion exchange membrane is used for an alkaline water electrolysis device.
1) An MEA of an electrolytic water device was prepared, and an anode and a cathode were prepared by a Catalyst Coated Substrate (CCS) method. The anode was prepared as follows: IrO is to be mixed2The powder was mixed with deionized water and isopropanol and then the PTFE emulsion was added. After 30 minutes of sonication, the catalyst ink was stirred in a water bath at 85 ℃ and water and isopropanol were evaporated. The paste obtained was coated on a platinized porous Ti plate. An ionomer solution (5 wt% solids copolymer in ethanol) was also sprayed onto the surface of the catalyst layer, drying the ionomer and IrO2The loading amounts in the anode were 1.5 and 8 mg-cm, respectively-2. For the preparation of the cathode, Pt/C (40 wt%), deionisedWater, isopropyl alcohol and PTFE emulsion (6 wt% in cathode) were mixed, and then the prepared ink was sonicated for 30 minutes and sprayed on carbon paper with a Pt loading of 0.4mg cm-2. The ionomer solution was also sprayed on the surface (1.5mg cm)-2). The electrode area is 8cm2. Finally, both electrodes and membrane were immersed in 1M NaOH for 24h for ion exchange and rinsed several times with deionized water before use;
2) the water electrolysis apparatus is assembled by sandwiching the membrane electrode between the cathode and the anode. A platinized porous Ti plate was used as a current collector in the cathode. Electrochemical tests were performed by soaking in anode and cathode deionized water, with the temperature maintained at 50 ℃. The polarization curve was obtained by measuring the cell voltage at different current densities and was measured at 50 ℃ and 200 mA-cm-2The durability thereof was evaluated at a constant current.
Example two
Under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding isatin monomer and N methyl-4-piperidone monomer, and dissolving the same in the solution, wherein the molar ratio of the two monomers is 1: 4, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
EXAMPLE III
Under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding isatin monomer and N-methyl-4-piperidone monomer, and dissolving the mixture in the solution in the same way, wherein the molar ratio of the two monomers is 1: 5.67, the solid content is controlled at 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example four
Under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding isatin monomer and N-methyl-4-piperidone monomer, and dissolving the mixture in the solution in the same way, wherein the molar ratio of the two monomers is 1: 9, the solid content is controlled to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
EXAMPLE five
Under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding isatin monomer and N-methyl-4-piperidone monomer, and dissolving the mixture in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example six:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare a transparent solution, then adding an isatin monomer and a 1- (5-chloropentyl) piperidine-4-ketone monomer, and dissolving the same in the solution, wherein the molar ratio of the two monomers is 1: 4, controlling the solid content to be 15 wt%. The remaining steps of this embodiment are the same as those of the first embodiment.
Example seven:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding isatin monomer and 1-ethylpiperidine-4-one monomer, and dissolving in the solution in the same way, wherein the molar ratio of the two monomers is 1: 4, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps in this example are the same as those in the first example.
Example eight:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding isatin monomer and N-methyl-4-piperidone monomer, and dissolving the mixture in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%; the rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example nine:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding 5-bromoindole-2, 3-diketone monomer and N-methyl-4-piperidone monomer, and dissolving in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example ten:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding phenanthrene-9, 10-diketone monomer and N-methyl-4-piperidone monomer, and dissolving the mixture in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example eleven:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding an acetonyl-1, 2-diketone monomer and an N-methyl-4-piperidone monomer, and dissolving the monomers in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example twelve:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare transparent solution, then adding 7-phenylindoline-2, 3-diketone monomer and N-methyl-4-piperidone monomer, and dissolving in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example thirteen:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare a transparent solution, then adding a 2-oxypropanoic acid monomer and an N-methyl-4-piperidone monomer, and dissolving the monomers in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example fourteen:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare a transparent solution, then adding a 1, 4-dibromobutane-2, 3-diketone monomer and an N-methyl-4-piperidone monomer, and dissolving the monomers in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example fifteen:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare a transparent solution, then adding a 3-bromo-2-oxopropanoic acid monomer and an N-methyl-4-piperidone monomer, and dissolving the monomers in the solution in the same manner, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example sixteen:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare a transparent solution, then adding a methyl 3,3, 3-trifluoro-2-oxopropanoate monomer and an N-methyl-4-piperidone monomer, and dissolving the monomers in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example seventeen:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare a transparent solution, then adding (E) -3- (hydroxyl amino) butane-2-ketone monomer and N-methyl-4-piperidone monomer, and dissolving the monomers in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Example eighteen:
under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare a transparent solution, then adding a benzil monomer and an N-methyl-4-piperidone monomer, and dissolving the benzil monomer and the N-methyl-4-piperidone monomer in the solution in the same way, wherein the molar ratio of the two monomers is 1: 19, controlling the solid content to be 15 wt%. The rest of the experimental steps and the application steps are the same as those in the first embodiment.
Comparative example:
this example uses as comparative examples a polymer which does not contain a diketone monomer when copolymerized: under the room temperature environment, firstly dissolving terphenyl in dichloromethane to prepare a transparent solution, then adding N-methyl-4-piperidone, and dissolving the mixture in the solution in the same way, wherein the molar ratio of two monomers is 1:1, controlling the solid content to be 15 wt%.
In summary, a comparison of the properties of the polymer films prepared in all examples and comparative examples is shown below.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. An anion exchange membrane containing arylene piperidine and diketone monomer copolymer is characterized in that: a copolymer comprising the following repeating structural units:
wherein Ar is a divalent organic group containing an aromatic ring, R1And R2Represent identical or different hydrocarbon radicals; x—Represents Br—、I—、Cl—、OH—、HCO3 —Or CO3 2-(ii) a n represents the degree of polymerization, n is a positive integer of 10-200, and the weight average molecular weight is 5000-800000; m is the mole percentage of the piperidine onium salt-containing part in the copolymer, and m is any number of 0-100.
2. The anion exchange membrane comprising a copolymer of arylene piperidine and diketone monomers according to claim 1, wherein:
ar is any one of the following groups:
containing R1，R2The radical piperidinium salts areAny one of the following groups:
containing R3，R4The carbonyl-containing matter of the group is any one of the following groups:
3. the method of claim 1 for preparing an anion exchange membrane comprising a copolymer of arylene piperidine and diketone monomers, comprising the steps of:
(1) firstly, dissolving aromatic hydrocarbon containing Ar groups in a dichloromethane solution at room temperature to prepare a transparent solution; then, adding a ketone monomer containing a piperidine ring and a diketone monomer into the dichloromethane solution, wherein the ketone monomer containing the piperidine ring and the diketone monomer are fully dissolved, the molar ratio of the ketone monomer containing the piperidine ring to the diketone monomer is 1:1-10, and the solid content is 10-20 wt%;
(2) dropwise adding trifluoroacetic acid and trifluoromethanesulfonic acid into the solution obtained in step (1) at 0 ℃, wherein the molar ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1:10.5, initiating polymerization at 0 ℃, and then reacting at room temperature for 2-24 h; after the polymerization reaction is finished, pouring the solution into methanol or ethanol to obtain a fibrous polymer, adding a potassium carbonate solution with the volume molar concentration of 1M after multiple times of precipitation and washing, and removing redundant acid in the solution; filtering, boiling the obtained fibrous solid polymer with water, filtering again, drying the obtained polymer in a vacuum drying oven at 60 ℃ for 24h, and weighing;
(3) and (3) dissolving the dried polymer in the step (2) in a polar solvent at 25-100 ℃, wherein the concentration of the polymer in the solution is 2-10 wt%, directly casting the obtained polymer solution on a glass plate or a stainless steel plate, flattening by using a casting knife, drying at 60-100 ℃ for 5-24h to form a film, and finally drying at 80-150 ℃ for 1-24h in vacuum to obtain the anion exchange membrane containing the arylene piperidine and diketone monomer copolymer.
4. The method for preparing an anion exchange membrane containing the copolymer of arylene piperidine and diketone monomer according to claim 3, wherein the method comprises the following steps: in the step (3), the polar solvent is one or more of NMP, DMF, DMAc, DMSO.
5. The method for preparing an anion exchange membrane containing the copolymer of arylene piperidine and diketone monomer according to claim 3, wherein the method comprises the following steps: in the step (3), the thickness of the prepared anion exchange membrane containing the arylene piperidine and diketone monomer copolymer is 10-100 mu m.
6. The use according to claim 1 of an anion exchange membrane comprising a copolymer of an arylenepiperidine and a diketone monomer, wherein: the anion exchange membrane is applied to an alkaline anion exchange membrane fuel cell or an alkaline anion exchange membrane water electrolysis device.
7. Use according to claim 6, characterized in that: the electrolyte in the alkaline water electrolysis device is one of potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate or pure water.
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