CN116272397B - Heterogeneous anion exchange membrane and device - Google Patents
Heterogeneous anion exchange membrane and device Download PDFInfo
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- CN116272397B CN116272397B CN202310427665.XA CN202310427665A CN116272397B CN 116272397 B CN116272397 B CN 116272397B CN 202310427665 A CN202310427665 A CN 202310427665A CN 116272397 B CN116272397 B CN 116272397B
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 105
- 239000000126 substance Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000000470 constituent Substances 0.000 claims abstract description 8
- -1 p-toluenesulfonyloxy, trifluoromethanesulfonic acid Chemical group 0.000 claims abstract description 8
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000005948 methanesulfonyloxy group Chemical group 0.000 claims abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 62
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 41
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 40
- 229960001545 hydrotalcite Drugs 0.000 claims description 40
- 238000005266 casting Methods 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 125000004970 halomethyl group Chemical group 0.000 claims description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims description 5
- 239000011147 inorganic material Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Chemical group 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 150000004693 imidazolium salts Chemical group 0.000 claims description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000005349 anion exchange Methods 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-O 1H-indol-1-ium Chemical group C1=CC=C2[NH2+]C=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-O 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical group C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical group C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical group C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical group C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical group C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 34
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical group ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 239000003014 ion exchange membrane Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 81
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 76
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 60
- 230000015572 biosynthetic process Effects 0.000 description 57
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 56
- 239000010410 layer Substances 0.000 description 42
- 238000003786 synthesis reaction Methods 0.000 description 37
- 239000012528 membrane Substances 0.000 description 29
- 239000000758 substrate Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000011521 glass Substances 0.000 description 25
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 23
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 239000002131 composite material Substances 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 18
- 239000003999 initiator Substances 0.000 description 17
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 16
- 239000002002 slurry Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- WLUJHMKCLOIRSK-UHFFFAOYSA-O 2,3,4,5-tetramethyl-1h-imidazol-3-ium Chemical group CC=1NC(C)=[N+](C)C=1C WLUJHMKCLOIRSK-UHFFFAOYSA-O 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- GNCJRTJOPHONBZ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1h-imidazole Chemical compound CC1(C)NC=NC1(C)C GNCJRTJOPHONBZ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000001226 reprecipitation Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical group O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000032895 transmembrane transport Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a heterogeneous anion exchange membrane and a device, wherein the ion exchange membrane comprises a polymer layer and an inorganic substance formed on the polymer layer, and the repeating units of the constituent materials of the polymer layer compriseThe general formula of the constituent materials of the polymer layer is:wherein, m is n= (0.5-9) 1; r1 is a positively charged cyclic amine group; x is selected from hydroxy, chloride, bromide, iodide, p-toluenesulfonyloxy, trifluoromethanesulfonic acid, methanesulfonyloxy. The product of the invention has good electrochemical performance and has good application in the fields of ion exchange, water electrolysis and the like.
Description
Technical Field
The present invention relates to electrochemical technology, and is especially one kind of heterogeneous anion exchange membrane and its device.
Background
Anion exchange membranes play an important role in the fields of electrolysis, electrodialysis, fuel cell technology, etc. Most of the current anion exchange membranes are obtained by copolymerizing monomers of various nonionic compounds, wherein the monomers having halomethyl functionality after polymerization react further with nitrogen containing bases via a gate Shu Tejin to form quaternary ammonium salts, e.g. WO2020250057A1, WO2021204890A1, etc. However, the polymerized system tends to leave a portion of the halomethyl functionality unreacted, such as WO2018204242A1, and the like. For anion exchange membranes, the transmembrane transport of anions is critical for the conductivity. Residual unreacted halomethyl functional groups do not promote conductivity and may also hinder pi interactions between cyclic amine functional groups, limiting the formation of microcrystalline regions and thus affecting the enhancement of conductivity of the film itself. At the same time, residual benzyl chloride may be replaced with benzyl alcohol, and further may be crosslinked. Thus making film preparation difficult to control.
In addition, for homogeneous anion exchange membranes, thin structures tend to give better electrochemical performance, but at the same time lead to problems with lower mechanical strength. Therefore, in the field of anion exchange membranes, the development of membrane materials with better electrochemical properties and simultaneously with controllable and scalable mechanical strength is an important challenge in commercial development.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a heterogeneous anion exchange membrane and a device, which effectively improve the performance of products in various aspects such as ion exchange, electrochemistry, strength and the like by optimizing the composition and the structure of the heterogeneous anion exchange membrane.
To achieve the above object, embodiments of the present invention provide a heterogeneous anion exchange membrane comprising a polymer layer and an inorganic substance formed on the polymer layer, the repeating unit of the constituent material of the polymer layer comprising、The general formula of the constituent materials of the polymer layer is:>wherein, m is n= (0.5-9) 1; r1 is a positively charged cyclic amine group; x is selected from hydroxy, chloride, bromide, iodide, p-toluenesulfonyloxy, trifluoromethanesulfonic acid, methanesulfonyloxy.
In one or more embodiments of the present invention, a heterogeneous anion exchange membrane includes a polymer layer and an inorganic formed on the polymer layer, the repeating units of the constituent materials of the polymer layer including、/>、The general formula of the constituent materials of the polymer layer is:
，
wherein, m is n= (0.5-9) 1; and satisfies the n, m, q together definition such that the total mass of the R2 corresponding monomers in the polymer layer is no more than 0.295%; r2 is selected from alkyl and halogen monosubstituted group thereof, wherein the alkyl is selected from methyl, ethyl, propyl and isopropyl, and the halogen is selected from chlorine, iodine and bromine; r1 is a positively charged cyclic amine group; x is selected from hydroxy, chloride, bromide, iodide, p-toluenesulfonyloxy, trifluoromethanesulfonic acid, methanesulfonyloxy. Preferably, m: n= (1.5-3): 1. Further preferably, m: n= (1.8-2.5): 1. Preferably, q/n is less than or equal to 0.95%. Preferably, R2 is selected from chloromethyl.
In the structural formula'"refers to the position of chain scission of a repeating unit.
In one or more embodiments of the invention, R1 is selected from the group consisting of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium. Preferably, R1 is selected from imidazolium. Further preferably, R1 is selected from tetramethylimidazolium.
In one or more embodiments of the invention, the inorganic material is selected from the group consisting of zirconia, titania, barium sulfate, magnesium hydroxide, nickel hydroxide, hydrotalcite, calcium carbonate. Preferably, the inorganic material is selected from the group consisting of zirconia, hydrotalcite, barium sulfate. It is further preferred that the mineral is selected from hydrotalcite, zirconia, i.e. preferably one or both combinations of the two. Further, the hydrotalcite is preferably MgAl-LDH or CaAl-LDH or ZnAl-LDH. Further, the hydrotalcite is Mg 12 Al 6 (OH) 36 (Mo 7 O 24 )H 2 O。
In one or more embodiments of the invention, the inorganic material is present in an amount of no more than 60wt.% of the polymer layer. Preferably, the inorganic is present in an amount of 10-30wt.% of the polymer layer. Preferably, the inorganic particles have a size of between 1nm and 1 μm. It is further preferred that the inorganic particles have a size of between 5nm and 500 nm. It is further preferred that the inorganic particles have a size of between 5nm and 200 nm.
In one or more embodiments of the present invention, the ion exchange membrane further comprises a porous support layer, and the polymer layer is formed on the porous support layer.
In one or more embodiments of the present invention, the material of the porous support layer is selected from the group consisting of polypropylene (PP), polyethylene (PE), polysulfone (PS), polyphenylene Sulfide (PPs), polyamide/nylon (PA), polyethersulfone (PEs), polyphenylene Sulfide (PPs), polyethylene terephthalate (PET), polyetheretherketone (PEEK), sulfonated polyetheretherketone (s-PEEK), expanded polytetrafluoroethylene (E-PTFE), chlorotrifluoroethylene (CTFE), a copolymer of Ethylene and Tetrafluoroethylene (ETFE), a copolymer of Ethylene and Chlorotrifluoroethylene (ECTFE), polyimide, polyetherimide and meta-aramid (m-aramid). EPTFE is preferred. Preferably, the porous support layer is a woven or nonwoven (e.g., porous membrane material, etc.).
In one or more embodiments of the invention, the porous support layer has a thickness of 1 to 60 μm. Further preferably, the porous support layer has a thickness of 2 μm to 40 μm.
In one or more embodiments of the invention, the porous support layer has a porosity of 40-90%. Preferably, the porous support layer has a porosity of 50 to 80%.
In one or more embodiments of the invention, the film has a thickness of 10-100 μm.
In one or more embodiments of the present invention, a method for preparing a heterogeneous anion exchange membrane includes the steps of preparing a polymer material and an inorganic substance of a polymer layer, and dispersing the polymer material and the inorganic substance in a solvent to form a uniform bubble-free casting solution; and (3) film forming and drying the film casting solution to obtain the heterogeneous anion exchange film. Preferably, the solvent can be one or a combination of several of toluene, ethanol, DMF, DMAc, DMSO and NMP. Preferably, the concentration range of the polymer raw material in the casting film liquid is 12-25%. Preferably, the inorganic substance accounts for 10-30% of the mass fraction of the polymer.
In one or more embodiments of the present invention, the casting solution may be uniformly applied to the surface of the substrate during film formation. Preferably, in the film forming process, after the porous supporting layer is paved on the surface of the substrate, the casting solution is uniformly coated on the surface of the substrate.
In one or more embodiments of the invention, the device comprises a heterogeneous anion exchange membrane as described previously. The device of the invention can be complete equipment or functional equipment or device parts forming the complete equipment, and the like, and mainly shows the application of the anion exchange membrane in the electrochemical field, namely, the device can be used as a part in the electrochemical process. The electrochemical process may include, but is not limited to, water electrolysis, electrodialysis, fuel cells, and the like.
Hydrotalcite materials belong to the class of anionic layered compounds. The lamellar compound is a compound with lamellar structure and interlayer ion exchange property, and by utilizing the intercalation property of lamellar compound host under the action of strong polar molecules and the exchange property of interlayer ion, some functional guest substances are introduced into interlayer gaps and the distance between layers is expanded so as to form the lamellar compound. Hydrotalcite-like compounds (LDHs) are novel inorganic functional materials with layered structures, and the chemical composition of main laminates of the LDHs is closely related to the factors such as the cationic characteristics of the laminates, the charge density of the laminates or the anion exchange capacity, the supermolecule intercalation structure and the like.
Compared with the prior art, the heterogeneous anion exchange membrane and the device provided by the embodiment of the invention can further additionally form the optimized combination of the high-strength porous support layer by providing the optimized combination of the high-ion-conductivity high-molecular structure and the hydrophilic inorganic filler with accurate proportion control, so that the heterogeneous anion exchange membrane structure with excellent electrochemical performance and good mechanical strength can be realized, and the influence of residual halomethylation functional groups on the ion conductivity and the electrochemical performance and on the parallelism and quality control of membrane preparation is avoided. The scheme selects a structure which does not contain or contains trace halomethyl functional group residues, can theoretically further improve the ion conductivity of the membrane and is convenient for controlling the membrane structure.
Drawings
FIG. 1 is a graph of ionic membrane electrical performance test according to one embodiment of the present invention (example A7);
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
Description: including but not limited to the examples below, where the initiator is defined as being based on the total monomer mass in the overall process, for example "1% mole of AIBN initiator" refers to the amount of initiator used to refer to the percentage of the total monomer mass in the system, i.e., where (m+n+q) is considered to be 1% mole, and where q is small or absent, it may be approximately (m+n) 1% mole.
Preparation of anion exchange membranes
The polymer obtained above was re-purified and then dissolved in DMF. Wherein the concentration range of the high molecular polymer is 12-25%, the zirconia accounts for 10-30% of the mass fraction of the polymer, and the solvent can be one or the combination of toluene, ethanol, DMF, DMAc, DMSO and NMP. The parts of the polymer, zirconia and DMF are respectively 2/0.3/10, the slurry is stirred uniformly, and the bubbles are removed in vacuum. And (3) paving the ePTFE film on a glass substrate flatly, uniformly coating the slurry on the ePTFE by using a Meier rod, putting the ePTFE film into a 120 ℃ oven for drying for 3 minutes, taking out the ePTFE film, putting the dried composite film into deionized water, and removing the film to obtain a final film product.
Electrochemical performance test
And (3) an anion membrane electrochemical test process, namely placing the prepared anion membrane in 30% KOH solution for 24 h, so that ions are replaced by hydroxyl. The ionic membrane is loaded with commercial Ru/C catalyst, 30% KOH is introduced into the anode, and air is directly introduced into the cathode, so that electrolytic water electrochemical test is carried out.
Example A1:
(A) Synthesis of polymers
The reaction was stopped after 1:1.2 equivalents of tetramethylimidazole and p-chloromethylstyrene in acetonitrile as solvent at 80℃for 1.5 days. The solid was purified to give vinylbenzyl-R1 monomer, R1 being tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomer and radical initiator were dissolved in a mixed solvent of 400. Mu.L toluene and 400. Mu.L ethanol. The mass ratio m: n of the styrene to the vinylbenzyl-R1 is 2:1. The mass of vinylbenzyl-R1 was 400mg. AIBN initiator amount 1% mole of the total monomer mass. The reaction temperature is 80 ℃ and the reaction time is 12 hours. The polymer obtained was purified by reprecipitation and then dissolved in DMF, the mass ratio of DMF to polymer being 10:2, and the crosslinking agent Divinylbenzene (DVB) being added. The amount of divinylbenzene was 10. Mu.L and reacted at 80℃for 12 hours.
Film formation
Adding hydrotalcite MgAl-LDH (Mg) 12 Al 6 (OH) 36 (Mo 7 O 24 )H 2 O, the same applies below), the mass ratio of polymer, hydrotalcite and DMF is 2:0.3:10. Hydrotalcite particles with a size of 50nm, the slurry was stirred well and the bubbles were removed in vacuo. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 70%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.78V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Comparative example: (B) Synthesis of polymers
As in example A1.
Film formation
The hydrotalcite MgAl-LDH is added into the obtained solution, and the mass ratio of the polymer to the hydrotalcite to the DMF is 2:0.3:10. Hydrotalcite particles with a size of 50nm, the slurry was stirred well and the bubbles were removed in vacuo. The casting solution was uniformly coated on a glass substrate using a 100 μm Meyer rod, and then put into an oven at 120℃for 3 minutes, and then taken out, and the dried composite film was put into deionized water for film removal, to obtain a film having a thickness of about 20. Mu.m.
Performance testing
Without the porous support layer, the membrane is extremely fragile and difficult to perform electrochemical tests
The comparative example provided in example A1 shows that the mechanical strength of the ion exchange membrane is significantly affected without a support layer.
Comparative example: (C) Synthesis of polymers
As in example A1.
Film formation
The solution obtained above was added with hydrotalcite MgAl-LDH (element content: C: 5: 5 wt%, O: 63: 63 wt%, mg:20wt%, al:12wt%, mass ratio of polymer, hydrotalcite and DMF was 2:0.3:10. Hydrotalcite particles with a size of 50nm, the slurry was stirred well and the bubbles were removed in vacuo. The casting solution was uniformly coated on a glass substrate using a 100 μm Meyer rod, and then put into an oven at 120℃for 3 minutes, and then taken out, and the dried composite film was put into deionized water for film removal, to obtain a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.97V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example A2:
synthesis of polymers
As in example A1.
Film formation
The hydrotalcite MgAl-LDH is added into the obtained solution, and the mass ratio of the polymer to the hydrotalcite to the DMF is 2:0.3:10. Hydrotalcite particles with a size of 1 μm were stirred uniformly and air bubbles were removed in vacuo. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 70%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 2.30V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example A3:
(A) Synthesis of polymers
As in example A1.
Film formation
The hydrotalcite MgAl-LDH is added into the obtained solution, and the mass ratio of the polymer to the hydrotalcite to the DMF is 2:0.3:10. Hydrotalcite particles with the size of 200nm are uniformly stirred, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 70%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.95V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example A4:
(A) Synthesis of polymers
As in example A1.
Film formation
The hydrotalcite MgAl-LDH is added into the obtained solution, and the mass ratio of the polymer to the hydrotalcite to the DMF is 2:0.3:10. Hydrotalcite particles with the size of 500nm are uniformly stirred, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 70%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 2.21V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example A5:
synthesis of polymers
As in example A1.
Film formation
Adding hydrotalcite CaAl-LDH (4 CaO-Al) into the obtained solution 2 O 3 -[Ca 2 Al(OH) 6 ]The same applies below), the mass ratio of polymer, hydrotalcite and DMF is 2:0.3:10. Hydrotalcite particles with the size of 200nm are uniformly stirred, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 70%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.97V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example A6:
synthesis of polymers
As in example A1.
Film formation
Adding hydrotalcite, polymer, hydrotalcite ZnAl-LDH (Zn) 0.5 Al 0.5 （CO3） 0.25 (OH) 2 ·H 2 O, the same as below) and DMF in a mass ratio of 2:0.3:10. Hydrotalcite particles with the size of 200nm are uniformly stirred, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 70%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 2.03V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example A7:
synthesis of polymers
As in example A1.
Film formation
Zirconia is added into the obtained solution, and the mass ratio of the polymer to the zirconia to the DMF is 2:0.3:10. The zirconia particles have a size of 50nm, the slurry is stirred uniformly, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 70%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.77v and the cell pressure did not rise by more than 5% over 500 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example A8:
synthesis of polymers
As in example A1.
Film formation
Barium sulfate is added into the obtained solution, and the mass ratio of the polymer to the barium sulfate to the DMF is 2:0.3:10. The particle size of barium sulfate is 50nm, the slurry is stirred uniformly, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 70%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.82V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example A9:
synthesis of polymers
As in example A1.
Film formation
Adding nickel hydroxide and an inorganic mixture with the mass ratio of hydrotalcite MgAl-LDH of 1:1 into the obtained solution, wherein the mass ratio of the polymer to the inorganic mixture to DMF is 2:0.3:10. The particle size of the inorganic mixture is 200nm, the slurry is stirred uniformly, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 70%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 2.10V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a10:
synthesis of polymers
As in example A1.
Film formation
Adding an inorganic mixture of magnesium hydroxide, zinc carbonate and nickel hydroxide in a mass ratio of 1:1:1 into the obtained solution, wherein the mass ratio of the polymer to the inorganic mixture to DMF is 2:0.3:10. The particle size of the inorganic mixture is 200nm, the slurry is stirred uniformly, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 70%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 2.13V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
As can be seen from the comparison of examples A1 to a10, the hydrotalcite MgAl-LDH, caAl-LDH, znAl-LDH, zirconia, and the like, which are obtained by optimizing the screening, show good synergistic effects on proton conductivity of the polymer according to the present embodiment, and the hydrotalcite structure and the zirconia have more remarkable effects than other types of inorganic substances as proton conductivity enhancing additive materials, so that the exchange membrane material can be enhanced as a whole.
Example a11:
synthesis of polymers
The reaction was stopped after 1:1.2 equivalents of tetramethylimidazole and p-chloromethylstyrene in acetonitrile as solvent at 80℃for 1.5 days. The solid was purified to give vinylbenzyl-R1 monomer, R1 being tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomer and radical initiator were dissolved in a mixed solvent of 400. Mu.L toluene and 400. Mu.L ethanol. The mass ratio m: n of styrene to vinylbenzyl-R1 is 0.5:1. The mass of vinylbenzyl-R1 was 400mg. AIBN initiator amount 1% mole of the total monomer mass. The reaction temperature is 80 ℃ and the reaction time is 12 hours. The polymer obtained was purified by reprecipitation and then dissolved in DMF, the mass ratio of DMF to polymer being 10:2, and the crosslinking agent Divinylbenzene (DVB) being added. The amount of divinylbenzene was 10. Mu.L and reacted at 80℃for 12 hours.
Film formation
Zirconia is added into the obtained solution, and the mass ratio of the polymer to the zirconia to the DMF is 2:1.2:10. The zirconia particles have a size of 50nm, the slurry is stirred uniformly, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 80%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.95V. The internal groove pressure rises by 5% after 100 h. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a12:
synthesis of polymers
The reaction was stopped after 1:1.2 equivalents of tetramethylimidazole and p-chloromethylstyrene in acetonitrile as solvent at 80℃for 1.5 days. The solid was purified to give vinylbenzyl-R1 monomer, R1 being tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomer and radical initiator were dissolved in a mixed solvent of 400. Mu.L toluene and 400. Mu.L ethanol. The mass ratio m of the styrene to the vinylbenzyl-R1 is 9:1. The mass of vinylbenzyl-R1 was 400mg. AIBN initiator amount 1% mole of the total monomer mass. The reaction temperature is 80 ℃ and the reaction time is 12 hours. The polymer obtained was purified by reprecipitation and then dissolved in DMF, the mass ratio of DMF to polymer being 10:2, and the crosslinking agent Divinylbenzene (DVB) being added. The amount of divinylbenzene was 10. Mu.L and reacted at 80℃for 12 hours.
Film formation
Zirconia is added into the obtained solution, and the mass ratio of the polymer to the zirconia to the DMF is 2:1.2:10. The zirconia particles have a size of 50nm, the slurry is stirred uniformly, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 80%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the electrolyzed water cell pressure was maintained at 2.10v and the cell pressure increased by about 5% for 300 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a13:
synthesis of polymers
The reaction was stopped after 1:1.2 equivalents of tetramethylimidazole and p-chloromethylstyrene in acetonitrile as solvent at 80℃for 1.5 days. The solid was purified to give vinylbenzyl-R1 monomer, R1 being tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomer and radical initiator were dissolved in a mixed solvent of 400. Mu.L toluene and 400. Mu.L ethanol. The mass ratio m: n of styrene to vinylbenzyl-R1 is 1.5:1. The mass of vinylbenzyl-R1 was 400mg. AIBN initiator amount 1% mole of the total monomer mass. The reaction temperature is 80 ℃ and the reaction time is 12 hours. The polymer obtained was purified by reprecipitation and then dissolved in DMF, the mass ratio of DMF to polymer being 10:2, and the crosslinking agent Divinylbenzene (DVB) being added. The amount of divinylbenzene was 10. Mu.L and reacted at 80℃for 12 hours.
Film formation
Zirconia is added into the obtained solution, and the mass ratio of the polymer to the zirconia to the DMF is 2:1.2:10. The zirconia particles have a size of 50nm, the slurry is stirred uniformly, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 80%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the electrolyzed water cell pressure was maintained at 1.90 v and the cell pressure increased by about 5% for 400 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a14:
synthesis of polymers
The reaction was stopped after 1:1.2 equivalents of tetramethylimidazole and p-chloromethylstyrene in acetonitrile as solvent at 80℃for 1.5 days. The solid was purified to give vinylbenzyl-R1 monomer, R1 being tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomer and radical initiator were dissolved in a mixed solvent of 400. Mu.L toluene and 400. Mu.L ethanol. The mass ratio m: n of the styrene to the vinylbenzyl-R1 is 3:1. The mass of vinylbenzyl-R1 was 400mg. AIBN initiator amount 1% mole of the total monomer mass. The reaction temperature is 80 ℃ and the reaction time is 12 hours. The polymer obtained was purified by reprecipitation and then dissolved in DMF, the mass ratio of DMF to polymer being 10:2, and the crosslinking agent Divinylbenzene (DVB) being added. The amount of divinylbenzene was 10. Mu.L and reacted at 80℃for 12 hours.
Film formation
Zirconia is added into the obtained solution, and the mass ratio of the polymer to the zirconia to the DMF is 2:1.2:10. The zirconia particles have a size of 50nm, the slurry is stirred uniformly, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 80%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the electrolyzed water cell pressure was maintained at 1.95v and the cell pressure increased by about 5% for 300 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a15:
synthesis of polymers
The reaction was stopped after 1:1.2 equivalents of tetramethylimidazole and p-chloromethylstyrene in acetonitrile as solvent at 80℃for 1.5 days. The solid was purified to give vinylbenzyl-R1 monomer, R1 being tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomer and radical initiator were dissolved in a mixed solvent of 400. Mu.L toluene and 400. Mu.L ethanol. The mass ratio m: n of styrene to vinylbenzyl-R1 is 1.8:1. The mass of vinylbenzyl-R1 was 400mg. AIBN initiator amount 1% mole of the total monomer mass. The reaction temperature is 80 ℃ and the reaction time is 12 hours. The polymer obtained was purified by reprecipitation and then dissolved in DMF, the mass ratio of DMF to polymer being 10:2, and the crosslinking agent Divinylbenzene (DVB) being added. The amount of divinylbenzene was 10. Mu.L and reacted at 80℃for 12 hours.
Film formation
Zirconia is added into the obtained solution, and the mass ratio of the polymer to the zirconia to the DMF is 2:1.2:10. The zirconia particles have a size of 50nm, the slurry is stirred uniformly, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 80%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the electrolyzed water cell pressure was maintained at 1.82v and the cell pressure increased by about 5% for 500 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a16:
synthesis of polymers
The reaction was stopped after 1:1.2 equivalents of tetramethylimidazole and p-chloromethylstyrene in acetonitrile as solvent at 80℃for 1.5 days. The solid was purified to give vinylbenzyl-R1 monomer, R1 being tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomer and radical initiator were dissolved in a mixed solvent of 400. Mu.L toluene and 400. Mu.L ethanol. The mass ratio m: n of styrene to vinylbenzyl-R1 is 2.5:1. The mass of vinylbenzyl-R1 was 400mg. AIBN initiator amount 1% mole of the total monomer mass. The reaction temperature is 80 ℃ and the reaction time is 12 hours. The polymer obtained was purified by reprecipitation and then dissolved in DMF, the mass ratio of DMF to polymer being 10:2, and the crosslinking agent Divinylbenzene (DVB) being added. The amount of divinylbenzene was 10. Mu.L and reacted at 80℃for 12 hours.
Film formation
Zirconia is added into the obtained solution, and the mass ratio of the polymer to the zirconia to the DMF is 2:1.2:10. The zirconia particles have a size of 50nm, the slurry is stirred uniformly, and bubbles are removed in vacuum. An ePTFE membrane with a thickness of 4 μm was used as the porous support layer with a porosity of about 80%. The ePTFE film was spread on a glass substrate flatly, the casting solution was uniformly coated on the ePTFE film using a 100 μm Meyer rod, and the film was taken out after drying in an oven at 120℃for 3 minutes, and the dried composite film was taken out in deionized water to give a film having a thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the electrolyzed water cell pressure was maintained at 1.84V and the cell pressure increased by about 5% for 400 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a17:
the only differences from a11 are: zirconium oxide is replaced by hydrotalcite in film forming processMgAl-LDH Mg 12 Al 6 (OH) 36 (Mo 7 O 24 )H 2 O。
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.97V. The internal groove pressure rises by 5% after 100 h. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a18:
the only differences from a12 are: zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg in film forming process 12 Al 6 (OH) 36 (Mo 7 O 24 )H 2 O。
Performance testing
At a current density of 400 mA, the electrolyzed water cell pressure was maintained at 2.11v and the cell pressure increased by about 5% for 300 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a19:
the only differences from a13 are: zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg in film forming process 12 Al 6 (OH) 36 (Mo 7 O 24 )H 2 O。
Performance testing
At a current density of 400 mA, the electrolyzed water cell pressure was maintained at 1.93v and the cell pressure increased by about 5% for 400 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a20:
the only differences from a14 are: zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg in film forming process 12 Al 6 (OH) 36 (Mo 7 O 24 )H 2 O。
Performance testing
At a current density of 400 mA, the electrolyzed water cell pressure was maintained at 1.98V and the cell pressure increased by about 5% for 300 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example a21:
the only differences from a15 are: zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg in film forming process 12 Al 6 (OH) 36 (Mo 7 O 24 )H 2 O。
Performance testing
At a current density of 400 mA, the electrolyzed water cell pressure was maintained at 1.84v and the cell pressure increased by about 5% for 500 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example A22
The only differences from a16 are: zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg in film forming process 12 Al 6 (OH) 36 (Mo 7 O 24 )H 2 O。
Performance testing
At a current density of 400 mA, the electrolyzed water cell pressure was maintained at 1.86V and the cell pressure increased by about 5% for 400 hours. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B11
The only difference from A1 (A) is that: in the synthesis of polymers
The mass ratio m of the substances of styrene, vinylbenzyl-R1 and p-vinylbenzyl chloride, n: q, is 2:1:0.009 (the mass fraction of R2 is 0.28%).
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.83V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B12
The only differences from a11 are: in the synthesis of polymers
The mass ratio m of the substances of styrene, vinylbenzyl-R1 and p-vinylbenzyl chloride, n: q, is 2:1:0.009 (the mass fraction of R2 is 0.28%).
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.93V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B13
The only differences from a17 are: in the synthesis of polymers
The mass ratio m of the substances of styrene, vinylbenzyl-R1 and p-vinylbenzyl chloride, n: q, is 2:1:0.009 (the mass fraction of R2 is 0.28%).
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.93V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B14
The only differences from A7 are: in the synthesis of polymers
The mass ratio m of the substances of styrene, vinylbenzyl-R1 and p-vinylbenzyl chloride, n: q, is 2:1:0.009 (the mass fraction of R2 is 0.28%).
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.83V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B21
The only differences from A2 are: in the synthesis of polymers
The mass ratio m of the substances of styrene, vinylbenzyl-R1 and p-vinylbenzyl chloride, n: q, is 2:1:0.0045 (mass fraction of R2 is 0.14%).
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 2.18V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B22
The only differences from a12 are: in the synthesis of polymers
The mass ratio m of the substances of styrene, vinylbenzyl-R1 and p-vinylbenzyl chloride, n: q, is 2:1:0.0045 (mass fraction of R2 is 0.14%).
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 2.03V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B23
The only differences from a18 are: in the synthesis of polymers
The mass ratio m of the substances of styrene, vinylbenzyl-R1 and p-vinylbenzyl chloride, n: q, is 2:1:0.0045 (mass fraction of R2 is 0.14%).
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 2.06V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B24
The only differences from A7 are: in the synthesis of polymers
The mass ratio m of the substances of styrene, vinylbenzyl-R1 and p-vinylbenzyl chloride, n: q, is 2:1:0.0045 (mass fraction of R2 is 0.14%).
Performance testing
The cell pressure was maintained at 1.77V at a current density of 400 mA. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B31
The only differences from A3 are: in the synthesis of polymers
The mass ratio m of the styrene, vinylbenzyl-R1 and the substance of the p-vinylbenzyl chloride is 2:1:0.003 (the mass fraction of R2 is 0.10%).
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.82V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B32
The only differences from a13 are: in the synthesis of polymers
The mass ratio m of the styrene, vinylbenzyl-R1 and the substance of the p-vinylbenzyl chloride is 2:1:0.003 (the mass fraction of R2 is 0.10%).
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.83V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B33
The only differences from a19 are: in the synthesis of polymers
The mass ratio m of the styrene, vinylbenzyl-R1 and the substance of the p-vinylbenzyl chloride is 2:1:0.003 (the mass fraction of R2 is 0.10%).
Performance testing
The cell pressure was maintained at 1.86V at a current density of 400 mA. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Example B34
The only differences from A7 are: in the synthesis of polymers
The mass ratio m of the styrene, vinylbenzyl-R1 and the substance of the p-vinylbenzyl chloride is 2:1:0.003 (the mass fraction of R2 is 0.10%).
Performance testing
The cell pressure was maintained at 1.73V at a current density of 400 mA. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Comparative example A1
Synthesis of polymers
The procedure for the polymer synthesis was exactly as in example A1 (A), without using inorganic hydrophilic material, the ePTFE film with a polymer to DMF ratio of 2:10,4 μm was spread flat on a glass substrate, the casting solution was applied uniformly to the glass substrate directly with a 100 μm Meyer rod, and after drying in an oven at 120℃for 3 minutes, the film was removed, and the dried composite film was taken out in deionized water to give a film thickness of about 20. Mu.m.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.93V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V. The mechanical strength of the membrane is weaker than that of the zirconia-added system.
Comparative example B1
The only differences from B11 are: in the synthesis of polymers
The mass ratio m of the styrene, vinylbenzyl-R1 and the substance of the p-vinylbenzyl chloride is 2:1:0.025 (the mass fraction of R2 is 0.62%).
Performance testing
The cell pressure was maintained at 1.95V at a current density of 400 mA. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Comparative example B2
The only differences from B11 are: in the synthesis of polymers
The mass ratio m of the substances of styrene, vinylbenzyl-R1 and p-vinylbenzyl chloride is 2:1:0.1 (the mass fraction of R2 is 3.0%).
Performance testing
The cell pressure was maintained at 2.10V at a current density of 400 mA. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Comparative example B3
The only differences from B14 are: in the synthesis of polymers
The mass ratio m of the styrene, vinylbenzyl-R1 and the substance of the p-vinylbenzyl chloride is 2:1:0.025 (the mass fraction of R2 is 0.62%).
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 1.92V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
Comparative example B4
The only differences from B14 are: synthesis of polymers
In the process of high molecular synthesis, other steps of styrene, vinylbenzyl-R1 and p-vinylbenzyl chloride with the ratio of 2:1:0.1 (3.0%) are identical to those of the example A1 (A), an ePTFE film with the ratio of polymer, zirconia and DMF with the ratio of 2:0.3:10 and 4 μm is flatly paved on a glass substrate, a 100 μm Meyer rod is directly used for uniformly coating a casting film liquid on the glass substrate, the glass substrate is put into a baking oven at 120 ℃ for drying for 3 minutes, then the glass substrate is taken out, and the dried composite film is put into deionized water for stripping, so that the film thickness of the film is about 20 μm.
Performance testing
At a current density of 400 mA, the cell pressure was maintained at 2.06V. The groove pressure of commercial film Fumasep-40 under equivalent test conditions was 2.10V.
As can be seen from the one-to-one matching comparison of the above examples and the comparative examples, the electrochemical performance of the product can be effectively improved by optimizing the polymer structure of the ionic membrane and the inorganic filler to optimize the corresponding scheme.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (8)
1. A heterogeneous anion exchange membrane comprises a support structure carrying a polymer layer and an inorganic substance formed on the polymer layer, wherein the repeating units of the constituent materials of the polymer layer comprise、/>、The general formula of the constituent materials of the polymer layer is:>wherein, m is n= (0.5-9) 1; and satisfies the n, m, q together definition such that the total mass of the R2 corresponding monomer structure in the polymer layer is not more than 0.295%; r2 is selected from halomethyl and halogen monosubstituted group thereof, halogen is selected from chlorine, iodine and bromine; r1 is a positively charged cyclic amine group; x is selected from chloride, bromide, iodide, p-toluenesulfonyloxy, trifluoromethanesulfonic acid, methanesulfonyloxy.
2. The heterogeneous anion exchange membrane of claim 1, wherein R1 is selected from the group consisting of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium.
3. The heterogeneous anion exchange membrane of claim 2, wherein R1 is selected from imidazolium.
4. The heterogeneous anion exchange membrane of claim 1, wherein the inorganic material is selected from the group consisting of zirconia, titania, barium sulfate, magnesium hydroxide, nickel hydroxide, hydrotalcite, and calcium carbonate.
5. The heterogeneous anion exchange membrane of claim 4, wherein the inorganic material is selected from at least one of zirconia and hydrotalcite.
6. The heterogeneous anion exchange membrane of claim 5, wherein the inorganic is present in an amount of no more than 60wt.% of the polymer layer.
7. The heterogeneous anion exchange membrane of any of claims 1-6, wherein the support structure is a porous support layer and the polymer layer is formed over the porous support layer.
8. A process for the preparation of a heterogeneous anion exchange membrane according to any one of claims 1 to 7, comprising the steps of:
preparing a polymer raw material and an inorganic substance of a polymer layer, and dispersing the polymer raw material and the inorganic substance in a solvent to form a uniform bubble-free casting solution;
and (3) forming a film and drying the film casting solution to obtain the heterogeneous anion exchange film.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124386A (en) * | 1973-10-24 | 1978-11-07 | Fuji Photo Film Co., Ltd. | Color diffusion transfer receiving layer comprising polymeric quaternary n-heterocyclic mordant |
| CN102179186A (en) * | 2011-03-10 | 2011-09-14 | 中国科学技术大学 | Monomer in situ polymerization-based homogeneous anion-exchange membrane and preparation method thereof |
| CN102206386A (en) * | 2011-04-02 | 2011-10-05 | 厦门大学 | Polymer anion-exchange membrane based on imidazole cation and preparation method thereof |
| KR20200139460A (en) * | 2019-06-04 | 2020-12-14 | 경상대학교산학협력단 | Anion-exchange composite membrane, preparation method thereof and fuel cell comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9370773B2 (en) * | 2010-07-04 | 2016-06-21 | Dioxide Materials, Inc. | Ion-conducting membranes |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124386A (en) * | 1973-10-24 | 1978-11-07 | Fuji Photo Film Co., Ltd. | Color diffusion transfer receiving layer comprising polymeric quaternary n-heterocyclic mordant |
| CN102179186A (en) * | 2011-03-10 | 2011-09-14 | 中国科学技术大学 | Monomer in situ polymerization-based homogeneous anion-exchange membrane and preparation method thereof |
| CN102206386A (en) * | 2011-04-02 | 2011-10-05 | 厦门大学 | Polymer anion-exchange membrane based on imidazole cation and preparation method thereof |
| KR20200139460A (en) * | 2019-06-04 | 2020-12-14 | 경상대학교산학협력단 | Anion-exchange composite membrane, preparation method thereof and fuel cell comprising the same |
Non-Patent Citations (1)
| Title |
|---|
| three-electrode study of electrochemical ionomer degradation relevant to anion-exchange-membrane water;Krivina, Raina A.等;ACS Applied Materials & Interfaces;第14卷(第16期);第18261-18274页 * |
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