CN114464854B - Preparation method of composite filling electrolyte membrane - Google Patents
Preparation method of composite filling electrolyte membrane Download PDFInfo
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- CN114464854B CN114464854B CN202011239348.8A CN202011239348A CN114464854B CN 114464854 B CN114464854 B CN 114464854B CN 202011239348 A CN202011239348 A CN 202011239348A CN 114464854 B CN114464854 B CN 114464854B
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- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 238000011049 filling Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003792 electrolyte Substances 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 33
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 33
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 23
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 23
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 20
- 239000012982 microporous membrane Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 11
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000643 oven drying Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000001326 spin-polarised Auger electron spectroscopy Methods 0.000 claims 10
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 16
- 239000004695 Polyether sulfone Substances 0.000 abstract description 6
- 229920006393 polyether sulfone Polymers 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- 239000011159 matrix material Substances 0.000 abstract 1
- 230000008961 swelling Effects 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000010521 absorption reaction Methods 0.000 description 15
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000003301 hydrolyzing effect Effects 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920006260 polyaryletherketone Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a preparation method of a composite filling electrolyte membrane. The method comprises the steps of taking a polytetrafluoroethylene microporous membrane as a matrix, immersing the PTFE microporous membrane into 73% sulfonated polyether ether ketone with high sulfonation degree or 50% sulfonated polyether sulfone solution with high sulfonation degree after hydrophilic treatment to obtain a filling membrane, immersing the filling membrane into 40% sulfonated polyether sulfone solution with low sulfonation degree to fix a filler, and treating the filling membrane with hydrochloric acid solution to obtain the composite filling proton exchange membrane. The preparation process is simple, and the prepared proton exchange membrane has excellent stability, good conductivity and other performances.
Description
Technical Field
The invention belongs to the technical field of preparation of proton exchange membranes, and relates to a preparation method of a composite filling electrolyte membrane.
Background
Fuel cells have been attracting attention for their advantages of high energy conversion efficiency and low pollution, where proton exchange membrane is one of the most important components in proton exchange membrane fuel cells. Classical perfluorinated sulfonic acid type proton exchange membranes such as Nafion series membranes from DuPont are difficult to overcome due to the fact that the membrane is easy to lose mechanical properties at high temperature, high methanol permeability and the like. The proton exchange membrane of hydrocarbon system has the advantages of low cost, good stability at high temperature, and the like and is of great concern. Common hydrocarbon polymers such as Sulfonated Polyketone (SPK), sulfonated Polyaryletherketone (SPAEK), sulfonated Polyarylethersulfone (SPAES), sulfonated polyaryletherketone sulfone (SPAEKS) and the like show good conductivity and battery performance in high Ion Exchange Capacity (IEC), but the high IEC brings defects of poor chemical stability, large expansibility in water and the like, so that the practical application in fuel cells is limited, and further research and improvement are necessary.
The filling type proton exchange membrane is a novel proton exchange membrane formed by filling electrolyte into a porous substrate membrane. Compared with the traditional perfluorinated sulfonic acid membrane, the filling type proton exchange membrane has the advantages of no swelling, low methanol permeability, high proton conductivity, low price, wide material selection range and the like. Document 1 (Journal of Membrane Science (2003) 283-292) proposes that a filled membrane is obtained by adding acrylic acid/sodium p-styrenesulfonate to a polytetrafluoroethylene porous membrane and copolymerizing the same, which can effectively improve the mechanical properties of the membrane and reduce the methanol permeability. However, due to the lower IEC, the conductivity level is not high; on the other hand, the crosslinking reaction process will result in insufficiently dense filling, voids still exist, and the fuel permeability is not necessarily high. Document 2 (Electrochimica Acta 307,307 (2019) 188-196) adopts sulfonated poly (arylene ether sulfone) with low sulfonation degree as a base film, alpha-cyclodextrin is added as a pore-forming agent in the film forming process, a microporous sulfonated poly (arylene ether sulfone) film with low sulfonation degree is formed after the pore-forming agent is removed, and the film is filled with tetrabutylammonium divinylbenzene sulfonate/N, N' -methylenebisacrylamide crosslinked polymer. As a certain amount of sulfonic acid groups are introduced into the base film, the IEC level is effectively improved, and the conductivity level is effectively improved while the mechanical stability of the film is maintained. However, the preparation method of the film is complicated and is not beneficial to large-scale production.
Disclosure of Invention
The invention provides a preparation method of a composite filling electrolyte membrane which is simple and easy to implement and has high stability and high conductivity.
The technical scheme of the invention is as follows:
The preparation method of the composite filling electrolyte membrane uses a commercial Polytetrafluoroethylene (PTFE) microporous membrane as a base membrane, and a high-sulfonation polyether ether ketone (SPEEK) or a high-sulfonation polyether sulfone (SPAES) polyelectrolyte is filled in the electrolyte membrane by a multi-impregnation method, and a low-sulfonation polyether sulfone (SPAES) is coated on the surface of the electrolyte membrane for fixing an internal filler, and the preparation method comprises the following specific steps:
Step 1, hydrophilic treatment of a polytetrafluoroethylene microporous membrane: soaking polytetrafluoroethylene microporous membrane in ethanol at room temperature for more than 30min, and oven drying;
Step 2, filling of sulfonated polyetheretherketone (SPEEK 73) or sulfonated polyarylethersulfone (SPAES, 50): at room temperature, soaking the PTFE microporous membrane subjected to hydrophilic treatment in an N, N-dimethylacetamide (DMAc) solution of SPEEK73 or SPAES, firstly soaking for 30min, and drying; soaking for 10min, and oven drying; finally soaking for 5min and drying; repeatedly soaking for 5min, and drying for more than 2 times;
Step 3, surface coating of sulfonated poly (arylene ether sulfone) (SPAES-40): immersing the PTFE film filled with SPEEK73 or SPAES50 in a DMAc solution of SPAES for 5min at room temperature, taking out and drying; the treatment times are 1-2 times;
Step 4, subsequent treatment of the filling film: and (3) vacuum drying the filling film obtained in the step (3) at 80 ℃, and finally soaking the filling film in 1mol/L HCl for 3d to exchange H +, thereby obtaining the composite filling electrolyte film.
Preferably, in step 1, the polytetrafluoroethylene microporous membrane has a pore size of 0.1 μm to 5. Mu.m.
Preferably, in step 2, the concentration of the SPEEK73 or SPAES50 solution is 5%, g/mL.
Preferably, in the step 2, soaking is performed for 5min, and the repetition number of drying is 4.
Preferably, in step3, SPAES solutions are used at a concentration of 8% g/mL.
Preferably, in step 3, SPAES times the surface is coated 2 times.
Compared with the prior art, the invention has the remarkable advantages that:
The polytetrafluoroethylene microporous membrane is used as a base membrane, the polytetrafluoroethylene microporous membrane endows the filled membrane with good mechanical property, and 73% of polyether-ether-ketone with high sulfonation degree or 50% of polyarylethersulfone with high sulfonation degree provides high conductivity; the 40% low sulfonation degree polyarylethersulfone ensures the stability of the endowed film; the membrane compactness and low fuel permeability are ensured by repeated dipping and 40% low-sulfonation degree polyarylethersulfone coating.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of sulfonated polyether ether ketone prepared in example 1.
FIG. 2 is an SEM image of each membrane, A being the surface of an unfilled PTFE membrane, D being the cross-section of the unfilled PTFE membrane, B being the surface of the PTFE membrane after filling with sulfonated polyether ether ketone; e is the section of the PTFE membrane filled with sulfonated polyether ether ketone, C is the surface of the PTFE membrane subjected to end capping by continuously sulfonated polyether sulfone, and F is the dense section of the PTFE membrane subjected to end capping.
In fig. 3, A, B, C is a graph of the water absorption, swelling ratio, proton conductivity and temperature change of the sulfonated polyether ether ketone filled membrane under different preparation conditions, and D is IEC under different preparation conditions.
FIG. 4 shows A, B, C shows the water absorption, swelling ratio and proton conductivity of sulfonated polyether-ether-ketone filled membranes with different pore diameters and the temperature change, and D shows the IEC with pore diameter.
FIG. 5 shows A, B, C shows the relationship between water absorption, swelling ratio and proton conductivity of Sulfonated Polyarylethersulfone (SPAES) filled membranes with different pore diameters and temperature, and D shows the relationship between IEC and pore diameter.
Table 1 shows the hydrolytic stability of sulfonated polyetheretherketone (SPEEK 73) filled membranes.
Table 2 shows the hydrolytic stability of sulfonated poly (arylene ether sulfone) (SPAES) filled membranes.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
Example 1
Synthesis of sulfonated polyetheretherketone (SPEEK 73):
Adopting a direct sulfonation method, wherein the raw material is polyether-ether-ketone, and the sulfonating agent is concentrated sulfuric acid; 5g of polyether-ether-ketone (PEEK) and 95mL of concentrated sulfuric acid are added into a 200mL round-bottom flask, dissolved for 1d at room temperature, heated to 45 ℃ and stirred for 10h, poured into an ice-water bath for cooling, washed with pure water until the washing liquid is neutral, and dried in a 60 ℃ oven. FIG. 1 is a nuclear magnetic spectrum of sulfonated polyether ether ketone, calculated from the nuclear magnetic spectrum, showing a sulfonation degree of 73% of SPEEK and a theoretical IEC of 2.11mmol/g.
Example 2
Synthesis of sulfonated polyarylethersulfone (SPAES, 50):
To a 100mL three-necked flask equipped with a nitrogen gas introducing apparatus, an oil-water separator and a condenser were successively added 1.1173g (6 mmol) of 4,4 '-Biphenol (BP), 0.7628g (3 mmol) of 4,4' -difluorodiphenyl sulfone (DFPDS), 1.3750g (3 mmol) of 3,3 '-sulfonic acid-4, 4' -difluorodiphenyl sulfone disodium salt (SDFDPS) and 13mL of dimethyl sulfoxide (DMSO). After complete dissolution 0.9536g (6.9 mmol) K 2CO3 and 13mL toluene were added. Slowly heating to 140 ℃ for reaction for 4 hours, and heating to 165 ℃ for reaction for 5 hours. After the reaction, the reaction product was cooled to room temperature, slowly poured into deionized water, a white fibrous solid was precipitated, repeatedly rinsed with deionized water, and dried in vacuo at 80 ℃ for 24 hours to give SPAES with a degree of sulfonation of 50%. According to the calculation SPAES theory IEC is 2.08mmol/g.
Example 3
Synthesis of sulfonated polyarylethersulfone (SPAES, 40):
To a 100mL three-necked flask equipped with a nitrogen gas introducing apparatus, an oil-water separator and a condenser were successively added 1.1173g (6 mmol) of 4,4 '-Biphenol (BP), 0.9153g (3.6 mmol) of 4,4' -difluorodiphenyl sulfone (DFPDS), 1.1000g (2.4 mmol) of 3,3 '-sulfonic acid-4, 4' -difluorodiphenyl sulfone disodium salt (SDFDPS) and 15mL of dimethyl sulfoxide (DMSO). After complete dissolution 0.9530g (6.9 mmol) K 2CO3 and 15mL toluene were added. Slowly heating to 140 ℃ for reaction for 4 hours, and heating to 165 ℃ for reaction for 5 hours. After the reaction, the reaction product was cooled to room temperature, slowly poured into deionized water, a white fibrous solid was precipitated, repeatedly rinsed with deionized water, and dried in vacuo at 80 ℃ for 24 hours to give SPAES with a degree of sulfonation of 40%. According to the calculation SPAES theory IEC is 1.72mmol/g.
Example 4
Preparation of the filling film:
And 1, hydrophilic treatment of the polytetrafluoroethylene microporous membrane. Soaking in absolute ethanol at room temperature for 30min, and drying in a vacuum oven for 30min. The pore diameters of the membranes used were 0.1 μm, 0.22 μm, 0.45 μm, 1 μm and 5 μm, respectively.
And 2, filling sulfonated polyether-ether-ketone or sulfonated polyether-ether-sulfone. SPEEK73 or SPAES was dissolved in DMAc to prepare a 5% (g/mL) solution. Soaking the PTFE film after hydrophilic treatment in a SPEEK73 or SPAES solution at room temperature for 30min, taking out, and airing in a 60 ℃ oven; (2) continuing to soak for 10min, taking out, and airing at 60 ℃; (3) Continuously soaking for 5 minutes, airing at 60 ℃, and (4) repeating the step (3) for 1-4 times.
And 3, coating the surface of the sulfonated polyarylethersulfone. SPAES 40A 40 was dissolved in DMAc to prepare an 8% (g/mL) solution of SPAES. The PTFE film filled with SPEEK73 or SPAES is immersed for 5min at room temperature, taken out, dried at 60 ℃, and the procedure is repeated 1-2 times.
And 4, carrying out subsequent treatment of the filling film. Drying in a vacuum oven at 80 ℃, soaking in 1mol/L HCl for 3d to exchange H + after drying, and obtaining the composite filling electrolyte membrane.
Comparative example 1
Preparation of a Membrane M0.45-113K (0) filled with sulfonated polyetheretherketone (SPEEK 73) alone: the preparation was identical to example 4, except that a pore size of 0.45 μm was used, which was not used in step 3, i.e. SPAES a with low sulfonation degree was not applied to the surface.
Comparative example 2
SPEEK73 filled film M0.45-113K (1) surface coated 1 times SPAES a 40 only: the preparation was the same as in example 4, except that no step 3 was employed, and SPAES times of 1 time of coating was performed on the surface.
TABLE 1 hydrolytic stability of SPEEK73 filled Membrane
Δσ% is the rate of change of proton conductivity measured at 80 °c
TABLE 2 hydrolytic stability of SPAES50 filled membranes
Δσ% is the rate of change of proton conductivity measured at 30 °c
The filled membranes prepared in the above examples and comparative examples were designated as Ma-bcdF (e), wherein a represents the pore size of the PTFE microporous membrane and b represents the number of times SPEEK73 or SPAES50 was immersed and filled for 30 min; c represents the soaking filling times of SPEEK73 after 10 min; d represents the number of times SPEEK73 or SPAES is filled by soaking for 5 min; f represents a filler material, where K is abbreviated as SPEEK73, S is abbreviated as SPAES, and e represents the number of coating applications of the film surface SPAES.
FIG. 2 is an SEM image of the films, A being the surface of the unfilled PTFE film, showing interlaced fibers, D being a cross-section of the unfilled PTFE film, showing a large number of unfilled voids; b is a smooth and flat surface of the PTFE film filled with sulfonated polyether ether ketone (SPEEK 73); e is the cross section of the PTFE membrane filled with sulfonated polyether ether ketone (SPEEK 73), C is the surface which is smooth and flat after the end capping of sulfonated polyether sulfone (SPAES) is carried out, and F is the dense cross section after the end capping.
FIG. 3 is a graph of water absorption, swelling ratio, and proton conductivity versus temperature for a sulfonated polyetheretherketone (SPEEK 73) filled membrane of different manufacturing conditions, respectively, A, B, C. D is IEC under different preparation conditions. As the impregnation times of the SPEEK73 are increased from 3 times to 6 times, the content of the SPEEK73 impregnated into the pores of the membrane is increased, IEC is increased continuously, the water absorption, the swelling rate and the proton conductivity are increased along with the increase, the water absorption of the membrane at 30 ℃ is 32.5% -45.0%, the plane swelling at 80 ℃ is 1.1% -1.7%, the section swelling is 3.6-12.6%, and the proton conductivity is 25.6-37.5 mS cm -1; as SPAES40 surface coating times are increased from 0 times to 2 times, IEC is slightly reduced due to the end capping, water absorption, swelling rate and proton conductivity are also reduced along with the increase, water absorption at 30 ℃ is 39.0-53.9%, plane swelling at 80 ℃ is 1.5-5.0%, section swelling is 8.7-16.7%, and proton conductivity is 37.2-41.7 mS cm -1.
Fig. 4 is a graph of water absorption, swelling ratio, proton conductivity versus temperature for a sulfonated polyetheretherketone (SPEEK 73) filled membrane of different pore sizes A, B, C, respectively. D is IEC as a function of pore size. The preparation conditions were 6 impregnations of SPEEK73 and 2 surface coatings of SPAES. As can be seen from the figure, the plane swelling level is low, the section swelling is significantly higher than the plane swelling, and the restriction of the PTFE template to the plane swelling is embodied. With the increasing of the pore diameter, the SPEEK73 content of the impregnated membrane pores is increased, IEC is increased, the water absorption, the swelling rate and the proton conductivity are increased, the water absorption at 30 ℃ is 29.9-47.9%, the plane swelling at 80 ℃ is 1.4-2.4%, the section swelling is 8.4-19.5%, and the proton conductivity is 23.2-61.2 mS cm -1.
In fig. 5, A, B, C is a graph of water absorption, swelling ratio, proton conductivity and temperature change of sulfonated poly (arylene ether sulfone) (SPAES 50) filled membranes with different pore diameters, respectively. D is IEC as a function of pore size. The preparation conditions are dipping 6 times SPAES and surface coating 2 times SPAES. As can be seen from the figure, the plane swelling level is low, the section swelling is significantly higher than the plane swelling, and the restriction of the PTFE template to the plane swelling is embodied. Along with the increasing of the pore diameter, the SPAES content of the impregnated membrane pores is increased, IEC is increased, the water absorption, the swelling rate and the proton conductivity are increased, the water absorption at 30 ℃ is 40.8-48.3%, the plane swelling at 80 ℃ is 2.1-4.2%, the section swelling is 7.9-25.7%, and the proton conductivity is 18.6-73.4 mS cm -1.
Table 1 shows the hydrolytic stability of sulfonated polyether ether ketone (SPEEK 73) filled membranes, the hydrolytic treatment conditions are 120 ℃, the treatment time is 24 hours, and the change rate delta sigma% of the proton conductivity of the membranes at 80 ℃ after the treatment is measured. All membranes exhibit a phenomenon of reduced proton conductivity. As SPAES surface coating times increased, hydrolytic stability increased as surface capping reduced water absorption. As the pore size of the membrane is continuously enlarged, the hydrolytic stability is continuously reduced. The larger the pore size, the more severe the SPEEK73 leakage and hydrolysis reaction.
Table 2 shows the hydrolytic stability of the sulfonated poly (arylene ether sulfone) (SPAES, 50) filled membranes, the treatment conditions for hydrolysis were 120℃for 24 hours, and the change rate Deltasigma% of the proton conductivity of the membranes at 30℃after treatment was measured. All membranes exhibit an increase in proton conductivity. The proton channel is more unblocked by high temperature water treatment, and SPAES of the soaked membrane pores absorb water and swell and then exude, and part of the water is blended with the surface layer SPAES.
Claims (4)
1. The preparation method of the composite filling electrolyte membrane is characterized by comprising the following specific steps:
Step 1, hydrophilic treatment of PTFE microporous membrane: soaking PTFE microporous membrane in ethanol at room temperature for more than 30min, and oven drying;
Step 2, filling of SPEEK73 or SPAES: at room temperature, soaking the PTFE microporous membrane subjected to hydrophilic treatment in a DMAc solution of SPEEK73 or SPAES, firstly soaking for 30min, and drying; soaking for 10min, and oven drying; finally soaking for 5min and drying; repeating the steps of soaking for 5min and drying for more than 2 times, wherein SPEEK73 is 73% of polyether ether ketone with high sulfonation degree, SPAES is 50% of polyarylethersulfone with sulfonation degree, and the concentration of DMAc solution of SPEEK73 or SPAES is 5%, g/mL;
Step 3, surface coating of SPAES 40: immersing the PTFE film filled with SPEEK73 or SPAES in a DMAc solution of SPAES for 5min at room temperature, taking out and drying; the treatment times are 1-2 times, SPAES percent of polyarylethersulfone with low sulfonation degree is 40 percent, the concentration of DMAc of SPAES percent is 8 percent, and g/mL;
Step 4, subsequent treatment of the filling film: and (3) vacuum drying the filling film obtained in the step (3) at 80 ℃, and finally soaking the filling film in 1 mol/L HCl for 3d to exchange H +, thereby obtaining the composite filling electrolyte film.
2. The method according to claim 1, wherein in step 1, the pore diameter of the PTFE microporous membrane is 0.1 μm to 5. Mu.m.
3. The preparation method according to claim 1, wherein in step 2, soaking is performed for 5min, and the number of repetitions of drying is 4.
4. The method according to claim 1, wherein the number of surface coating steps of SPAES to 40 in step 3 is 2.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110054607A (en) * | 2009-11-18 | 2011-05-25 | 한국화학연구원 | Reinfored composite electrolyte membrane and manufacturing method thereof |
| CN102838743A (en) * | 2012-08-29 | 2012-12-26 | 南京理工大学 | Preparation method of sulfonated hydrophilic oligomer and blocked sulfonated polymer as well as blocked cross-linked sulfonated polyether sulphone proton exchange membrane |
| CN102838746A (en) * | 2012-08-29 | 2012-12-26 | 南京理工大学 | Preparation method and application of sulfonated polyarylether sulfone polymer and sulfonated polyarylether sulfone cation exchange membrane |
| CN105406091A (en) * | 2015-12-25 | 2016-03-16 | 湖北工程学院 | Preparing method of polyvinylidene fluoride-heteropoly acid-chitosan composite proton exchange membrane |
| CN109742429A (en) * | 2018-12-21 | 2019-05-10 | 南京理工大学 | The preparation method of filled-type proton exchange membrane |
-
2020
- 2020-11-09 CN CN202011239348.8A patent/CN114464854B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110054607A (en) * | 2009-11-18 | 2011-05-25 | 한국화학연구원 | Reinfored composite electrolyte membrane and manufacturing method thereof |
| CN102838743A (en) * | 2012-08-29 | 2012-12-26 | 南京理工大学 | Preparation method of sulfonated hydrophilic oligomer and blocked sulfonated polymer as well as blocked cross-linked sulfonated polyether sulphone proton exchange membrane |
| CN102838746A (en) * | 2012-08-29 | 2012-12-26 | 南京理工大学 | Preparation method and application of sulfonated polyarylether sulfone polymer and sulfonated polyarylether sulfone cation exchange membrane |
| CN105406091A (en) * | 2015-12-25 | 2016-03-16 | 湖北工程学院 | Preparing method of polyvinylidene fluoride-heteropoly acid-chitosan composite proton exchange membrane |
| CN109742429A (en) * | 2018-12-21 | 2019-05-10 | 南京理工大学 | The preparation method of filled-type proton exchange membrane |
Non-Patent Citations (5)
| Title |
|---|
| "Four-polymer blend proton exchange membranes derived from sulfonated poly(aryl ether sulfone)s with various sulfonation degrees for application in fuel cells";Alphonse Haragirimana等;《Journal of Membrane Science》;20191231;全文 * |
| "填充型质子交换膜的制备与性能研究";王若谕;《CNKI硕士学位论文 工程科技I辑》;20230115;全文 * |
| Shouyi Liu,等."PTFE-reinforced pore-filling proton exchange membranes with sulfonated poly(ether ether ketone)s and poly(aryl ether sulfone)s".《Journal of Membrane Science》.2024,全文. * |
| 填充型具有微孔结构的磺化聚芳醚砜/聚醚砜复合质子交换膜的制备及性能;朱雨昕;HARAGIRIMANA Alphonse;陆瑶;BUREGEYA Ingabire Providence;宁聪;李娜;胡朝霞;陈守文;;高等学校化学学报;20190510(第05期);全文 * |
| 朱雨昕 ; HARAGIRIMANA Alphonse ; 陆瑶 ; BUREGEYA Ingabire Providence * |
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