CN116646574A - Polymer modified composite proton exchange membrane, preparation method thereof and fuel cell - Google Patents
Polymer modified composite proton exchange membrane, preparation method thereof and fuel cell Download PDFInfo
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- CN116646574A CN116646574A CN202310514858.9A CN202310514858A CN116646574A CN 116646574 A CN116646574 A CN 116646574A CN 202310514858 A CN202310514858 A CN 202310514858A CN 116646574 A CN116646574 A CN 116646574A
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- exchange membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 136
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 239000000446 fuel Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 title claims description 29
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 71
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 64
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 64
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 230000001590 oxidative effect Effects 0.000 claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 claims abstract description 33
- 239000007800 oxidant agent Substances 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 230000005588 protonation Effects 0.000 claims abstract description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 238000010345 tape casting Methods 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000557 Nafion® Polymers 0.000 abstract description 26
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- 238000011049 filling Methods 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 230000008595 infiltration Effects 0.000 abstract description 5
- 238000001764 infiltration Methods 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000002441 reversible effect Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000010410 layer Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 238000012685 gas phase polymerization Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
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- 238000012986 modification Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000002225 anti-radical effect Effects 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012808 vapor phase Substances 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
-
- 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
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity 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
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a macromolecule modified composite proton exchange membrane, a preparation method thereof and a fuel cell. The preparation method comprises the following steps: soaking porous polytetrafluoroethylene bulks into oxidant dispersion liquid, and then taking out and drying; coating polypyrrole on the porous polytetrafluoroethylene expanded surface in a gas-phase oxidation polymerization mode; and coating a perfluorinated sulfonic acid resin solution on the surface of the porous polytetrafluoroethylene bulked body coated and modified by the PPy nano-particles, and then drying, heat treatment and protonation treatment to obtain the composite proton exchange membrane. According to the invention, the porous polytetrafluoroethylene bulks are modified by polypyrrole to improve the infiltration characteristic of the porous polytetrafluoroethylene bulks to the resin solution, so that the efficient filling of Nafion resin is ensured; the protonated PPy has a certain proton conductivity, so that the proton conductivity of the composite membrane can be effectively improved; the existence of PPy can be used as a reversible reducer to relieve the chemical corrosion of strong oxidative oxygen free radicals to Nafion resin, and improve the durability of the composite proton exchange membrane.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a polymer modified composite proton exchange membrane, a preparation method thereof and a fuel cell.
Background
A proton exchange membrane fuel cell is an energy conversion device capable of directly converting chemical energy in hydrogen fuel and oxidant into electric energy through electrochemical reaction. The fuel cell has the characteristics of high energy conversion efficiency, no exhaust emission and the like, is considered as one of the most promising schemes for solving energy crisis and environmental pollution, and particularly has great application prospects in the aspects of transportation such as automobiles, ships, standby power supplies and the like. Because of these outstanding advantages, the development and application of fuel cell technology are emphasized, and are considered to be the first clean and efficient power generation mode in the 21 st century.
The proton exchange membrane is one of the core materials of the membrane electrode of the fuel cell, and plays important roles in conducting protons, separating cathode and anode, supporting a catalytic layer and preventing gas from crossing each other in the fuel cell. The structural stability and durability of proton exchange membranes have a critical impact on fuel cell performance and life. In order to improve the mechanical strength and the swelling resistance of the proton exchange membrane, porous polytetrafluoroethylene (e-PTFE) is generally adopted as a reinforced swelling body, and Nafion resin is filled and coated in the swelling body to obtain the composite proton exchange membrane. Since e-PTFE is highly hydrophobic, nafion dispersion is difficult to fully infiltrate into the pores of the expanded mass to form an effective fill. Strategy for solving chemical corrosion problemOften incorporating anti-radical additives, e.g. CeO 2 Pt, etc., reduce the strongly oxidizing radicals, thereby alleviating the oxidative corrosion of the perfluorosulfonic acid resin by the radicals.
CN1861668A improves the hydrophilicity of the porous polytetrafluoroethylene membrane by a plasma treatment method, so that the perfluorinated sulfonic acid resin solution and the porous polytetrafluoroethylene membrane are better combined, and the mechanical strength and proton conductivity of the prepared composite proton exchange membrane are improved. CN1706540a adopts the mode of gas pressure to make proton conducting resin fully enter into porous high polymer matrix, so as to promote the performance of composite proton exchange membrane. CN112599825 a adopts a magnetron sputtering mode to sputter a layer of uniformly dispersed Pt particles on one surface of the porous PTFE membrane, so as to improve the oxidation corrosion resistance of the composite proton exchange membrane. However, the above methods cannot achieve both improvement of resin wettability and oxidation corrosion resistance through a single treatment.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a polymer modified composite proton exchange membrane, a preparation method thereof and a fuel cell, which solve the technical problem that the resin wettability, the proton conductivity and the oxidation corrosion resistance of the proton exchange membrane cannot be simultaneously improved in a single treatment mode in the prior art.
In a first aspect, the present invention provides a method for preparing a polymer modified composite proton exchange membrane, comprising the steps of:
soaking the porous polytetrafluoroethylene bulks into oxidant dispersion liquid, and then taking out and drying the porous polytetrafluoroethylene bulks to enable the porous polytetrafluoroethylene bulks to be attached with the oxidant;
coating polypyrrole on the porous polytetrafluoroethylene bulked body in a gas-phase oxidation polymerization mode to obtain a PPy nanoparticle coated modified porous polytetrafluoroethylene bulked body;
and coating a perfluorinated sulfonic acid resin solution on the surface of the porous polytetrafluoroethylene bulked body coated and modified by the PPy nano-particles, and then drying, heat treatment and protonation treatment to obtain the composite proton exchange membrane.
In a second aspect, the present invention provides a polymer modified composite proton exchange membrane, which is obtained by the preparation method of the polymer modified composite proton exchange membrane provided in the first aspect of the present invention.
In a third aspect, the present invention provides a fuel cell comprising the polymer modified composite proton exchange membrane of the second aspect of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the porous polytetrafluoroethylene bulks are modified by polypyrrole, so that the infiltration characteristic of the porous polytetrafluoroethylene bulks to a resin solution is improved, the infiltration of the Nafion solution in the porous polytetrafluoroethylene bulks is further improved, and the high-efficiency filling of the Nafion resin is ensured; in addition, the protonated PPy has certain proton conductivity, so that the proton conductivity of the composite membrane can be effectively improved; meanwhile, the existence of PPy can be used as a reversible reducer to relieve the chemical corrosion of strong oxidative oxygen free radicals on Nafion resin, so that the durability of the composite proton exchange membrane is improved.
Drawings
FIG. 1 is a scanning electron microscope image of the microstructure of a porous polytetrafluoroethylene bulked body coated and modified by PPy nanoparticles prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope picture of the cross-sectional microstructure of the composite proton exchange membrane prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope picture of the cross-sectional microstructure of the composite proton exchange membrane prepared in comparative example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of the microstructure of the PPy nanoparticle coated modified porous polytetrafluoroethylene bulge prepared in comparative example 2;
fig. 5 is a scanning electron microscope picture of a cross-sectional microstructure of the composite proton exchange membrane prepared in comparative example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In a first aspect, the present invention provides a method for preparing a polymer modified composite proton exchange membrane, comprising the steps of:
s1, soaking the porous polytetrafluoroethylene bulks into oxidant dispersion liquid, and then taking out and drying the porous polytetrafluoroethylene bulks to enable the porous polytetrafluoroethylene bulks to be attached with an oxidant;
s2, coating polypyrrole (PPy) on the porous polytetrafluoroethylene expanded surface in a gas-phase oxidation polymerization mode to obtain a porous polytetrafluoroethylene expanded body coated and modified by PPy nano particles;
s3, coating a perfluorinated sulfonic acid resin solution on the surface of the porous polytetrafluoroethylene bulked body coated and modified by the PPy nano-particles, and then drying, heat treatment and protonizing to obtain the composite proton exchange membrane.
According to the invention, a conductive polypyrrole nano coating layer is doped and introduced into a porous polytetrafluoroethylene membrane in a gas-phase oxidation polymerization mode, and then a perfluorinated sulfonic acid resin solution is coated on the surface of an e-PTFE membrane to obtain the composite proton exchange membrane. Polypyrrole is a polymer material with reversible oxidation-reduction performance and has hydrophilic performance obviously superior to that of an e-PTFE membrane, so that a perfluorinated sulfonic acid resin solution can well infiltrate into the e-PTFE membrane modified by the polypyrrole and fully infiltrate into holes of the e-PTFE membrane to form the composite proton exchange membrane with high resin filling degree. Meanwhile, polypyrrole introduced into the e-PTFE membrane can be used as a reducing agent to react with an oxygen radical intermediate with strong oxidability generated in the running process of the battery, so that Nafion resin is protected from being corroded by oxidation, and the chemical durability of the proton exchange membrane is improved. In addition, the protonated PPy has certain proton conductivity, and can effectively improve the proton conductivity of the composite membrane. In addition, unlike other inorganic anti-free radical additives, polypyrrole is taken as a nitrogenous polymer material, and rich N atoms on a molecular chain of the polypyrrole can form hydrogen bond action with Nafion resin, so that the polypyrrole nano particles and the Nafion resin are tightly combined, and the problems of migration, agglomeration, loss and the like can not occur along with the progress of the reaction. Through the improvement of the invention, the resin filling efficiency in the preparation process of the bulked reinforced composite proton exchange membrane can be effectively improved, and the proton conductivity, the oxidation corrosion resistance and the durability of the composite proton exchange membrane are improved.
In this embodiment, the porous polytetrafluoroethylene bulk has a thickness of 5-15 μm; the pore size is 100-1000nm, and further 200-1000nm.
In this embodiment, the oxidizing agent is at least one of ammonium persulfate, ferric chloride, and potassium dichromate. Further, in the oxidant dispersion, the solvent used is a mixture of water and alcohol, wherein the alcohol can be one of ethanol, n-propanol and isopropanol; the concentration of the oxidant is 0.01-1mol/L, and the ratio of the surface area of the porous polytetrafluoroethylene bulks to the oxidant dispersion is 0.1-1cm 2 /mL。
In this embodiment, the porous polytetrafluoroethylene bulks are immersed in the oxidizer dispersion for 1 to 30 minutes.
In this embodiment, the gas-phase oxidation polymerization is carried out by: the pyrrole monomer is contacted with an oxidant attached to the surface of the porous polytetrafluoroethylene expansion body in a vacuum volatilization mode, and the pyrrole monomer is oxidized and polymerized by the oxidant to obtain the PPy nanoparticle coated and modified porous polytetrafluoroethylene expansion body.
In some embodiments of the present invention, the step of coating the porous polytetrafluoroethylene expanded surface with polypyrrole by vapor phase oxidative polymerization comprises: placing pyrrole monomer dispersion liquid and porous polytetrafluoroethylene bulks with oxidants attached to the surfaces in a vacuum oven, vacuumizing to volatilize pyrrole monomers to the surfaces of the porous polytetrafluoroethylene bulks, performing oxidative polymerization by the oxidants, and then performing full water washing and alcohol washing and drying to obtain the PPy nanoparticle coated modified porous polytetrafluoroethylene bulks. Further, in the pyrrole monomer dispersion liquid, the mass fraction of the pyrrole monomer is 5-50wt%, and the ratio of the surface area of the porous polytetrafluoroethylene bulks to the oxidant dispersion liquid is 1-10cm 2 The vacuum degree is below-50 kPa, the temperature of the gas phase oxidation polymerization is 20-40 ℃, and the time of the gas phase oxidation polymerization is 5-60min.
In some embodiments of the present invention, the perfluorosulfonic acid resin solution is obtained by dispersing a perfluorosulfonic acid resin at high temperature and high pressure.
In this embodiment, the mass fraction of the perfluorosulfonic acid resin solution is 5wt% to 40wt%, and the particle diameter of the perfluorosulfonic acid resin clusters is in the range of 100 to 300nm, and further 100 to 150nm.
In the embodiment, the perfluorosulfonic acid resin solution is coated on the surface of the porous polytetrafluoroethylene bulked body coated and modified by PPy nano particles by a normal temperature and normal pressure blade coating mode. Compared with the dipping-drying coating mode, the coating mode adopts a blade coating mode, the resin filling and film forming effects are better, and the cracking is reduced.
In this embodiment, the perfluorosulfonic acid resin solution is applied at a thickness of 30 to 200. Mu.m.
In this embodiment, the heat treatment temperature is 100-250deg.C, and the heat treatment time is 10-90min. The invention is beneficial to improving the crystallinity of the perfluorinated sulfonic acid resin in the proton membrane by heat treatment, thereby improving the swelling resistance and the heat stability of the proton exchange membrane.
In this embodiment, the step of protonating includes: immersing the proton exchange membrane after heat treatment into H of 0.1-1mol/L 2 SO 4 Soaking at 50-80deg.C for 20-40min, taking out, and repeatedly washing the membrane with deionized water; repeating the above process for 2-3 times, airing the proton membrane at normal temperature, and then carrying out gradient heating drying treatment at 60-100 ℃ to obtain the protonated composite proton exchange membrane.
In a second aspect, the present invention provides a polymer modified composite proton exchange membrane, which is obtained by the preparation method of the polymer modified composite proton exchange membrane provided in the first aspect of the present invention.
In a third aspect, the present invention provides a fuel cell comprising the polymer modified composite proton exchange membrane of the second aspect of the present invention.
Example 1
The embodiment provides a preparation method of a polymer modified composite proton exchange membrane, which comprises the following steps:
(1) 5 μm thick porous polytetrafluoroethylene bulks (e-PTFE, 8cm x 10cm, average pore diameter 300 nm) were placed in 200ml of 0.1mol/L ferric chloride dispersion (the solvent is a mixed solution of water and ethanol in a volume ratio of 7:3) and immersed for 30min, and then taken out and dried, so that the bulks were sufficiently adhered with the oxidant.
(2) And (3) placing 20ml of pyrrole monomer dispersion liquid with the mass fraction of 30wt% (the solvent is deionized water) and the e-PTFE bulks treated by the oxidant in a vacuum oven, vacuumizing to the vacuum degree of-80 kPa at the oven temperature of 30 ℃, coating a layer of polypyrrole (PPy) nano particles on the porous polytetrafluoroethylene bulks in a gas-phase oxidation polymerization mode, carrying out gas-phase oxidation polymerization for 30min, and drying after the gas-phase polymerization reaction is finished after full water washing and ethanol washing to obtain the PPy nano particle coated and modified e-PTFE bulks.
(3) Dispersing perfluorinated sulfonic acid resin at high temperature and high pressure to obtain 20wt% of perfluorinated sulfonic acid resin (Nafion, the average size of resin clusters is 150 nm) solution, respectively coating a layer of Nafion dispersion liquid with the thickness of 100 mu m on two sides of a PPy nanoparticle coated and modified e-PTFE expansion body in a normal temperature and normal pressure doctor-blading mode, drying at normal temperature, and further carrying out heat treatment and protonation treatment to obtain a composite proton exchange membrane material; wherein the heat treatment temperature is 200 ℃, and the heat treatment time is 30min; the protonizing treatment steps are as follows: immersing the proton exchange membrane after heat treatment into H with the concentration of 0.5mol/L at 60 DEG C 2 SO 4 Soaking for 30min, taking out, and repeatedly washing the membrane with deionized water; repeating the above process for 3 times, airing the proton membrane at normal temperature, and then carrying out gradient heating drying treatment at 60-100 ℃ to obtain the protonated composite proton exchange membrane.
Example 2
The embodiment provides a preparation method of a polymer modified composite proton exchange membrane, which comprises the following steps:
(1) 5 μm thick porous polytetrafluoroethylene bulks (e-PTFE, 8cm x 10cm, average pore diameter 300 nm) were placed in 200ml of 0.1mol/L ferric chloride dispersion (the solvent is a mixed solution of water and ethanol in a volume ratio of 7:3) and immersed for 30min, and then taken out and dried, so that the bulks were sufficiently adhered with the oxidant.
(2) And (3) placing 20ml of pyrrole monomer dispersion liquid with the mass fraction of 50wt% (the solvent is deionized water) and the e-PTFE bulks treated by the oxidant in a vacuum oven, vacuumizing to the vacuum degree of-80 kPa at the oven temperature of 30 ℃, coating a layer of polypyrrole (PPy) nano particles on the porous polytetrafluoroethylene bulks in a gas-phase oxidation polymerization mode, carrying out gas-phase oxidation polymerization for 15min, and drying after the gas-phase polymerization reaction is finished after full water washing and ethanol washing to obtain the PPy nano particle coated and modified e-PTFE bulks.
(3) Dispersing perfluorinated sulfonic acid resin at high temperature and high pressure to obtain 15wt% of perfluorinated sulfonic acid resin (Nafion, average size of resin clusters is 120 nm) solution, respectively coating a layer of Nafion dispersion liquid with 140 mu m on two sides of a PPy nanoparticle coated and modified e-PTFE expansion body in a normal temperature and normal pressure doctor-blading mode, drying at normal temperature, and further carrying out heat treatment and protonation treatment to obtain a composite proton exchange membrane material; wherein the heat treatment temperature is 200 ℃, and the heat treatment time is 30min; the protonizing treatment steps are as follows: immersing the proton exchange membrane after heat treatment into H with the concentration of 0.5mol/L at 60 DEG C 2 SO 4 Soaking for 30min, taking out, and repeatedly washing the membrane with deionized water; repeating the above process for 3 times, airing the proton membrane at normal temperature, and then carrying out gradient heating drying treatment at 60-100 ℃ to obtain the protonated composite proton exchange membrane.
Example 3
The embodiment provides a preparation method of a polymer modified composite proton exchange membrane, which comprises the following steps:
(1) 5 μm thick porous polytetrafluoroethylene bulks (e-PTFE, 8cm x 10cm, average pore diameter 300 nm) were placed in 200ml of 0.5mol/L ferric chloride dispersion (the solvent is a mixed solution of water and ethanol in a volume ratio of 7:3) and soaked for 10min, and then taken out and dried, so that the bulks were sufficiently adhered with the oxidant.
(2) And (3) placing 20ml of pyrrole monomer dispersion liquid with the mass fraction of 20wt% (the solvent is deionized water) and the e-PTFE bulks treated by the oxidant in a vacuum oven, vacuumizing to the vacuum degree of-80 kPa at the oven temperature of 30 ℃, coating a layer of polypyrrole (PPy) nano particles on the porous polytetrafluoroethylene bulks in a gas-phase oxidation polymerization mode, carrying out gas-phase oxidation polymerization for 50min, and drying after the gas-phase polymerization reaction is finished after full water washing and ethanol washing to obtain the PPy nano particle coated and modified e-PTFE bulks.
(3) Dispersing perfluorinated sulfonic acid resin at high temperature and high pressure to obtain 20wt% of perfluorinated sulfonic acid resin (Nafion, the average size of resin clusters is 150 nm) solution, respectively coating a layer of Nafion dispersion liquid with the thickness of 100 mu m on two sides of a PPy nanoparticle coated and modified e-PTFE expansion body in a normal temperature and normal pressure doctor-blading mode, drying at normal temperature, and further carrying out heat treatment and protonation treatment to obtain a composite proton exchange membrane material; wherein the heat treatment temperature is 200 ℃, and the heat treatment time is 30min; the protonizing treatment steps are as follows: immersing the proton exchange membrane after heat treatment into H with the concentration of 0.5mol/L at 60 DEG C 2 SO 4 Soaking for 30min, taking out, and repeatedly washing the membrane with deionized water; repeating the above process for 3 times, airing the proton membrane at normal temperature, and then carrying out gradient heating drying treatment at 60-100 ℃ to obtain the protonated composite proton exchange membrane.
Comparative example 1
The comparative example provides a preparation method of a composite proton exchange membrane, which comprises the following steps:
dispersing perfluorinated sulfonic acid resin at high temperature and high pressure to obtain 20wt% of perfluorinated sulfonic acid resin (Nafion, the average size of resin clusters is 150 nm), respectively coating a layer of Nafion dispersion liquid with the thickness of 100 μm on two sides of 5 mu m porous polytetrafluoroethylene bulks (e-PTFE, 8cm x 10cm, the average pore diameter of 300 nm) in a normal temperature and normal pressure blade coating mode, drying at normal temperature, and further carrying out heat treatment and protonation treatment to obtain a composite proton exchange membrane material; wherein the heat treatment temperature is 200 ℃, and the heat treatment time is 30min; the protonizing treatment steps are as follows: immersing the proton exchange membrane after heat treatment into H with the concentration of 0.5mol/L at 60 DEG C 2 SO 4 Soaking for 30min, taking out, and repeatedly washing the membrane with deionized water; repeating the above process for 3 times, airing the proton membrane at normal temperature, and then carrying out gradient heating drying treatment at 60-100 ℃ to obtain the protonated composite proton exchange membrane.
Comparative example 2
The comparative example provides a preparation method of a polymer modified composite proton exchange membrane, which comprises the following steps:
(1) 5 μm thick porous polytetrafluoroethylene bulks (e-PTFE, 8cm x 10cm, average pore diameter 300 nm) were placed in 200ml of 0.1mol/L ferric chloride dispersion (the solvent is a mixed solution of water and ethanol in a volume ratio of 7:3) and immersed for 30min, and then taken out and dried, so that the bulks were sufficiently adhered with the oxidant.
(2) Placing the porous polytetrafluoroethylene bulks treated by the oxidant into 60ml of 0.1mol/L pyrrole monomer dispersion liquid (the solvent is deionized water), fully soaking, controlling the reaction temperature to be 30 ℃, loading polypyrrole particles on the bulks in a liquid-phase oxidation polymerization mode, taking out the bulks after the polymerization reaction is finished, and drying after fully washing with water and ethanol to obtain the PPy nanoparticle coated modified e-PTFE bulks.
(3) Dispersing perfluorinated sulfonic acid resin at high temperature and high pressure to obtain 20wt% of perfluorinated sulfonic acid resin (Nafion, the average size of resin clusters is 150 nm) solution, respectively coating a layer of Nafion dispersion liquid with the thickness of 100 mu m on two sides of a PPy nanoparticle coated and modified e-PTFE expansion body in a normal temperature and normal pressure doctor-blading mode, drying at normal temperature, and further carrying out heat treatment and protonation treatment to obtain a composite proton exchange membrane material; wherein the heat treatment temperature is 200 ℃, and the heat treatment time is 30min; the protonizing treatment steps are as follows: immersing the proton exchange membrane after heat treatment into H with the concentration of 0.5mol/L at 60 DEG C 2 SO 4 Soaking for 30min, taking out, and repeatedly washing the membrane with deionized water; repeating the above process for 3 times, airing the proton membrane at normal temperature, and then carrying out gradient heating drying treatment at 60-100 ℃ to obtain the protonated composite proton exchange membrane.
Referring to fig. 1, fig. 1 is a scanning electron microscope image of a microstructure of a porous polytetrafluoroethylene bulked body coated and modified with PPy nanoparticles prepared in example 1 of the present invention. As can be seen from FIG. 1, the fibrous structure surface of the e-PTFE membrane is loaded with a layer of nanoparticles, while a better retention of the pore structure of the e-PTFE membrane is observed.
Referring to fig. 2, fig. 2 is a scanning electron microscope image of a cross-sectional microstructure of the composite proton exchange membrane prepared in example 1 of the present invention. As can be seen from fig. 2, the e-PTFE layer in the middle of the composite proton exchange membrane has been completely filled with resin particles and no significant voids are observed.
In contrast, referring to fig. 3, fig. 3 is a scanning electron microscope picture of a cross-section microstructure of the composite proton exchange membrane prepared in comparative example 1 of the present invention. As can be seen from FIG. 3, the e-PTFE in the middle of the composite proton exchange membrane has poor filling degree and very obvious gap and layering phenomena, which fully shows that the coating of PPy nano particles on the e-PTFE membrane obviously improves the infiltration characteristic of the PPy nano particles on Nafion resin, thereby improving the filling degree of the resin in the composite membrane. Obviously, the higher the filling degree of the resin particles in the e-PTFE, the better the mechanical strength and the anti-swelling performance of the prepared composite proton exchange membrane.
Referring to fig. 4, fig. 4 is a scanning electron microscope image of a microstructure of the porous polytetrafluoroethylene bulks coated and modified with PPy nanoparticles prepared in comparative example 2 of the present invention. As can be seen from FIG. 4, the polypyrrole nanoparticles are largely agglomerated and attached to the surface of the e-PTFE film, almost completely covering the fiber pore structure, and the fiber structure inside the e-PTFE film can be seen only from the remaining small amount of pore structure. The reason for this phenomenon is that: the e-PTFE membrane in the reaction system has poor intrinsic hydrophobicity, and pyrrole monomers are difficult to infiltrate into the pore diameter of the bulked body rapidly and fully in the liquid phase reaction process, so that the problem of poor polymerization uniformity is aggravated. Obviously, uneven loading of polypyrrole necessarily affects the impregnating effect of the resin in the next process.
Referring to fig. 5, fig. 5 is a scanning electron microscope picture of a cross-sectional microstructure of the composite proton exchange membrane prepared in comparative example 2 of the present invention. As can be seen from FIG. 5, the e-PTFE in the composite proton membrane prepared in comparative example 2 has poor filling degree and obvious delamination.
The following table 1 compares the key performance parameters such as mechanical strength, proton conductivity, hydrogen permeation current, etc. of the composite proton exchange membranes prepared in example 1 and comparative examples 1 to 2, and the change conditions of the performance indexes before and after oxidation corrosion. The method for testing parameters such as thickness, conductivity, tensile strength, hydrogen permeation current and the like refers to the national standard GB/T20042.3-2009 proton exchange membrane fuel cell part 3: proton exchange membrane test methods.
TABLE 1 Key performance parameters for composite proton exchange membranes of example 1 and comparative examples 1-2, variation before and after oxidative corrosion
As can be seen from Table 1, the conductivity, tensile strength and hydrogen permeation current data of the PPy modified composite proton exchange membrane (example 1) obtained by the gas phase polymerization reaction are superior to those of the PPy modified composite proton exchange membrane (comparative example 1) which is not subjected to PPy modification and the PPy modified composite proton exchange membrane (comparative example 2) obtained by the liquid phase polymerization reaction, which shows that the PPy coating treatment process based on the gas phase polymerization reaction is more beneficial to improving the interface contact and infiltration problem of the e-PTFE membrane and the Nafion solution, improving the filling degree of Nafion resin particles in the e-PTFE membrane, further improving the tensile strength and the conductivity of the composite membrane, and simultaneously, the higher filling degree can slow down the permeation of hydrogen and reduce the hydrogen permeation current.
As can be seen from the change results of key characteristic parameters after the Fenton reagent (hydrogen peroxide solution and ferrous ion solution) oxidation corrosion test, after the oxidation corrosion is carried out for 100 hours, the thickness, the conductivity, the tensile strength and the hydrogen permeation current data of the composite proton exchange membrane of the embodiment 1 are slightly changed, while the thickness, the conductivity and the tensile strength of the composite proton exchange membrane of the comparative example 1 and the comparative example 2 are obviously reduced after the oxidation corrosion is carried out for 100 hours, and meanwhile, the hydrogen permeation current is sharply increased. This is because the resin filling degree of the composite proton exchange membrane in example 1 is higher, and PPy nano particles loaded on the e-PTFE membrane can be used as a reducing agent to react with a strong oxidizing group, so that the corrosive decomposition effect of the Fenton reagent on the perfluorinated sulfonic acid resin particles in the composite proton exchange membrane is reduced, and the stability of various performance indexes of the composite proton exchange membrane is ensured.
In addition, as can be seen from the results of comparative examples 1 and 2, the conductivity, tensile strength, hydrogen permeation current effect and oxidation corrosion effect of the composite proton exchange membrane of comparative example 2 are all worse than those of comparative example 1, and it can be further demonstrated by combining the above analysis demonstration that although the reasonable introduction of the polypyrrole modification layer can improve the filling degree, conductivity, oxidation corrosion resistance and other capacities of the composite proton exchange membrane, if a proper polypyrrole introduction method is not adopted, the problem that the polypyrrole particles block the pore diameter of polytetrafluoroethylene can occur, thereby seriously affecting the effective filling of the perfluorosulfonic acid resin cluster particles in the subsequent treatment process, and leading to no adverse drop in various performances and durability indexes of the synthesized proton exchange membrane. Therefore, a practical and effective implementation strategy is provided, the reasonable distribution of the polypyrrole modification layer in the polytetrafluoroethylene bulks is ensured, the advantages of hydrophilicity, oxidation resistance, conductivity and the like of the polypyrrole can be fully exerted, the filling degree of the perfluorinated sulfonic acid resin in the bulks after the polypyrrole modification is effectively improved, the mechanical property, conductivity and oxidation resistance of the finished product composite proton exchange membrane are further improved, and the hydrogen permeation current is reduced.
The result shows that the pretreatment of the e-PTFE membrane by using the PPy in a gas-phase oxidation polymerization mode can effectively improve the wettability of Nafion solution in the e-PTFE, ensure the efficient filling of Nafion resin, and the protonated PPy has a certain proton conductivity, so that the proton conductivity of the composite membrane can be effectively improved, and meanwhile, the existence of the PPy can be used as a reversible reducing agent to relieve the chemical corrosion of strong oxidative oxygen free radicals on the Nafion resin, so that the durability of the composite proton exchange membrane is improved.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any of various other corresponding changes and modifications made according to the technical idea of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. The preparation method of the polymer modified composite proton exchange membrane is characterized by comprising the following steps of:
soaking the porous polytetrafluoroethylene bulks into oxidant dispersion liquid, and then taking out and drying the porous polytetrafluoroethylene bulks to enable the porous polytetrafluoroethylene bulks to be attached with the oxidant;
coating polypyrrole on the porous polytetrafluoroethylene expanded surface in a gas-phase oxidation polymerization mode to obtain a PPy nanoparticle coated modified porous polytetrafluoroethylene expanded body;
and coating a perfluorinated sulfonic acid resin solution on the surface of the porous polytetrafluoroethylene bulked body coated and modified by the PPy nano-particles, and then drying, heat treatment and protonation treatment to obtain the composite proton exchange membrane.
2. The method for preparing a polymer modified composite proton exchange membrane according to claim 1, wherein the porous polytetrafluoroethylene bulks have a thickness of 5-15 μm and a pore size of 100-1000nm.
3. The method for preparing a polymer modified composite proton exchange membrane according to claim 1, wherein the oxidant in the oxidant dispersion liquid is at least one of ammonium persulfate, ferric chloride and potassium dichromate; the solvent is a mixture of water and alcohol; the concentration of the oxidant is 0.01-1mol/L; the porous polytetrafluoroethylene bulks are soaked into the oxidant dispersion liquid for 1-30min.
4. The method for preparing a polymer modified composite proton exchange membrane according to claim 1, wherein the step of coating polypyrrole on the porous polytetrafluoroethylene expanded surface by gas phase oxidative polymerization comprises: placing pyrrole monomer dispersion liquid and porous polytetrafluoroethylene bulks with oxidants attached to the surfaces in a vacuum oven, vacuumizing to volatilize pyrrole monomers to the surfaces of the porous polytetrafluoroethylene bulks, performing oxidative polymerization by the oxidants, and then performing full water washing and alcohol washing and drying to obtain the PPy nanoparticle coated modified porous polytetrafluoroethylene bulks.
5. The method for preparing a polymer modified composite proton exchange membrane according to claim 4, wherein the mass fraction of pyrrole monomer in the pyrrole monomer dispersion is 5-50wt%, the vacuum degree is below-50 kPa, the gas phase oxidation polymerization temperature is 20-40 ℃, and the gas phase oxidation polymerization time is 5-60min.
6. The method for preparing a polymer modified composite proton exchange membrane according to claim 1, wherein the mass fraction of the perfluorinated sulfonic acid resin solution is 5wt% -40wt%, and the particle size of the perfluorinated sulfonic acid resin cluster is 100-300nm.
7. The preparation method of the polymer modified composite proton exchange membrane according to claim 1, wherein the porous polytetrafluoroethylene bulked surface coated and modified by PPy nano particles is coated with a perfluorinated sulfonic acid resin solution by a normal temperature and pressure doctor-blading method; the coating thickness of the perfluorinated sulfonic acid resin solution is 30-200 μm.
8. The method for preparing a polymer modified composite proton exchange membrane according to claim 1, wherein the heat treatment temperature is 100-250 ℃ and the heat treatment time is 10-90min; the step of protonating includes: immersing the proton exchange membrane after heat treatment into H of 0.1-1mol/L 2 SO 4 Soaking at 50-80deg.C for 20-40min, taking out, and repeatedly washing the membrane with deionized water; repeating the above process for 2-3 times, airing the proton membrane at normal temperature, and then carrying out gradient heating drying treatment at 60-100 ℃ to obtain the protonated composite proton exchange membrane.
9. A polymer modified composite proton exchange membrane, characterized in that the polymer modified composite proton exchange membrane is obtained by the preparation method of the polymer modified composite proton exchange membrane according to any one of claims 1 to 8.
10. A fuel cell comprising the polymer modified composite proton exchange membrane of claim 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117117270A (en) * | 2023-10-23 | 2023-11-24 | 国家电投集团氢能科技发展有限公司 | Modified porous membrane, ion exchange membrane, preparation method and application of modified porous membrane and ion exchange membrane, and fuel cell |
| CN117343369A (en) * | 2023-12-04 | 2024-01-05 | 武汉氢能与燃料电池产业技术研究院有限公司 | Preparation method of perfluorosulfonic acid composite proton exchange membrane material |
| CN117913331A (en) * | 2024-03-14 | 2024-04-19 | 中海储能科技(北京)有限公司 | Proton exchange membrane modification method for iron-chromium flow battery and perfluorinated sulfonic acid composite membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117117270A (en) * | 2023-10-23 | 2023-11-24 | 国家电投集团氢能科技发展有限公司 | Modified porous membrane, ion exchange membrane, preparation method and application of modified porous membrane and ion exchange membrane, and fuel cell |
| CN117117270B (en) * | 2023-10-23 | 2024-02-09 | 国家电投集团氢能科技发展有限公司 | Modified porous membrane, ion exchange membrane, preparation method and application of modified porous membrane and ion exchange membrane, and fuel cell |
| CN117343369A (en) * | 2023-12-04 | 2024-01-05 | 武汉氢能与燃料电池产业技术研究院有限公司 | Preparation method of perfluorosulfonic acid composite proton exchange membrane material |
| CN117343369B (en) * | 2023-12-04 | 2024-03-12 | 武汉氢能与燃料电池产业技术研究院有限公司 | Preparation method of perfluorosulfonic acid composite proton exchange membrane material |
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