CN113471496A - High-proton conductivity high-strength perfluorosulfonic acid composite proton exchange membrane and preparation method thereof - Google Patents
High-proton conductivity high-strength perfluorosulfonic acid composite proton exchange membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 136
- 239000002131 composite material Substances 0.000 title claims abstract description 111
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 85
- 229920005989 resin Polymers 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 59
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 36
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- 229920005597 polymer membrane Polymers 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 46
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000001132 ultrasonic dispersion Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 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
-
- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength and a preparation method thereof, wherein the preparation method comprises the following steps: s1: coating the perfluorinated sulfonic acid resin solution on two sides of the porous enhancement layer in a solution casting manner, repeating for 2-4 times, and drying the solvent to obtain an enhanced composite membrane; s2: fully emulsifying the sulfonated carbon nanotubes and a perfluorinated sulfonic acid resin solution, and then carrying out ultrasonic mixing to obtain a perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated carbon nanotubes; s3: and coating perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated carbon nanotubes on two sides of the reinforced composite membrane in a solution casting manner, and drying the solvent to obtain the perfluorinated sulfonic acid composite proton exchange membrane with high proton conductivity and high strength. Compared with the prior art, the invention realizes the preparation of the enhanced proton exchange membrane by three-layer network compounding, obviously improves the mechanical strength of the composite proton exchange membrane, and can effectively improve the proton conductivity of the proton exchange membrane by doping modification of the sulfonated carbon nanotube.
Description
Technical Field
The invention relates to the field of proton exchange membrane preparation, in particular to a perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength and a preparation method thereof.
Background
At present, the homogeneous perfluorosulfonic acid proton exchange membrane is difficult to adapt to various complicated requirements of the fuel cell (such as humidity, temperature, mechanical property, intramembrane water transfer of electromigration water and back diffusion water, and the like), and especially the homogeneous proton exchange membrane swells under the condition of multiple alternation of dry and wet to cause the mechanical strength to be reduced and fail, which is extremely unfavorable for the long-term application of the homogeneous perfluorosulfonic acid proton exchange membrane with a thinner thickness in the fuel cell. In order to improve the mechanical stability of the proton exchange membrane, the mechanical reinforced composite proton exchange membrane is industrially prepared by polymerizing perfluorinated sulfonic acid resin or hydrocarbon ions and compounding a porous Polytetrafluoroethylene (PTFE) membrane. Meanwhile, the PTFE enhanced thin proton exchange membrane is applied to a fuel cell, which is not only beneficial to obviously reducing the internal resistance of the cell to improve the performance of the cell, but also greatly reduces the consumption of the perfluorinated sulfonic acid resin and obviously reduces the manufacturing cost.
The enhanced proton exchange membrane becomes the development trend at the present stage, on one hand, the matrix enhancement layer can be ultra-thinned, the proton conduction resistance is greatly reduced, the ohmic polarization is reduced, and the power density of the electric pile is improved; on the other hand, the base membrane is thin and still has high mechanical strength, so that the base membrane can play a good role in enhancing the perfluorinated sulfonic acid proton exchange membrane, and the durability and the mechanical stability of the composite proton exchange membrane are improved. However, the proton conductivity of the composite membrane is somewhat lowered due to the introduction of a reinforcing material component (porous PTFE-based membrane) of the non-proton conductor. Therefore, how to improve the proton conductivity of the perfluorosulfonic acid ion exchange membrane on the premise of enhancing the mechanical strength is always the direction of the researchers.
The method has the advantages that the sulfonated graphene is adopted for doping modification in the Chinese patent CN111875825A, so that the proton conductivity of the ion exchange membrane can be obviously improved, the problem of high swelling rate of the existing homogeneous ion exchange membrane can be effectively solved due to the introduction of the porous reinforcing material, the mechanical strength of the ion exchange membrane can be greatly improved, but the porous structure of PTFE is blocked by the flaky sulfonated graphene, so that the sulfonic acid resin cannot be completely filled, and gaps are formed. In addition, sulfonated graphene in the sulfonic acid resin solution cannot completely and uniformly infiltrate and fill the porous PTFE base membrane micropores, so that the performance of the fuel cell is affected due to the uneven distribution of the sulfonated graphene in the thickness direction of the composite proton exchange membrane.
In conclusion, inorganic particles doped in the preparation process of the composite proton exchange membrane are easy to block micropores of the base membrane and cannot be uniformly dispersed in the micropore structure, so that the preparation of a high-performance proton exchange membrane is not facilitated, and a problem to be solved is needed.
Disclosure of Invention
The invention aims to solve the problems and provide a high proton conductivity and high strength perfluorosulfonic acid composite proton exchange membrane and a preparation method thereof, which remarkably improve the mechanical strength of the composite proton exchange membrane and can effectively improve the proton conductivity of the proton exchange membrane through doping modification of sulfonated carbon nanotubes.
The purpose of the invention is realized by the following technical scheme:
the first purpose of the application is to protect a preparation method of a high-proton conductivity and high-strength perfluorosulfonic acid composite proton exchange membrane, which comprises the following steps:
s1: coating the perfluorinated sulfonic acid resin solution on two sides of the porous enhancement layer in a solution casting manner, repeating for 2-4 times, and drying the solvent to obtain an enhanced composite membrane;
s2: fully emulsifying the sulfonated carbon nanotubes and a perfluorinated sulfonic acid resin solution, and then carrying out ultrasonic mixing to obtain a perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated carbon nanotubes;
s3: and (3) coating the perfluorinated sulfonic acid resin solution with the uniformly dispersed sulfonated carbon nanotubes obtained in the step (S2) on two sides of the reinforced composite membrane in a solution casting manner, and drying the solvent to obtain the perfluorinated sulfonic acid composite proton exchange membrane with high proton conductivity and high strength.
Further, the porous reinforcing layer material in S1 is one or a combination of several of polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, and polyethylene.
Further, in S1, the amount of the perfluorosulfonic acid resin solution is controlled so that the thickness of the reinforced composite film after coating is substantially the same as that before coating, and the reinforced composite film is completely densely filled in the thickness direction.
Furthermore, the porosity of the porous enhancement layer in S1 is 80-95%, and the thickness is 2-20 μm.
Further, the solvent in the perfluorinated sulfonic acid resin solution in S1 and S2 is one or a mixed solvent of n-propanol, water, ethanol and dimethyl sulfoxide, wherein the solid content of the perfluorinated sulfonic acid resin is 2-25 wt.%.
Further, the solid content of the sulfonic acid resin in S2 is lower than or equal to S1.
Further, the sulfonated carbon nanotube in S2 is a single-walled or multi-walled carbon nanotube, the sulfonated carbon nanotube has a length of 5-50 μm and a tube diameter of 5-50 nm, and the content of S element in the sulfonated carbon nanotube is 0.05-15 wt.%.
Further, the addition amount of the sulfonated carbon nanotubes in the sulfonated carbon nanotube doped layer in S2 is 0.01-10 wt% of the perfluorosulfonic acid resin.
Further, in S3, a carbon nanotube reinforced network and a proton conduction network are constructed on the surface of the reinforced composite membrane through a perfluorinated sulfonic acid resin solution in which sulfonated carbon nanotubes are uniformly dispersed, and the reinforced proton exchange membrane is prepared by three-layer network compounding by combining a polymer membrane porous network of a reinforced composite membrane matrix.
Further, the emulsification process comprises the following steps: emulsifying at high speed for 1-20 min by using an emulsifying machine, and preferably for 1-10 min;
the ultrasonic time is 1-60 min, and preferably 1-25 min;
the drying temperature in S1 and S3 is 30-200 ℃, the drying temperature is preferably 50-150 ℃, and the drying time is 10-30 min.
Further, the solution casting method in S1 and S3 is: adopting one or more of knife coating, slit extrusion, comma scraper, dip coating, spray coating and the like.
The second purpose of the application is to protect the perfluorinated sulfonic acid composite proton exchange membrane with high proton conductivity and high strength, which is obtained by the preparation method, and the thickness of the composite proton exchange membrane is 5-30 μm.
Compared with the prior art, the invention has the beneficial effects that:
1) on the basis of introducing a porous base membrane as an enhancement layer, firstly coating pure perfluorinated sulfonic acid resin on the surface of the porous base membrane to prepare a densely filled enhanced composite membrane, then coating perfluorinated sulfonic acid resin doped with sulfonated carbon nano tubes on the surface of the porous base membrane to construct a double-network structure of the carbon nano tubes, and finally forming the enhancement layer with a three-network structure in the composite proton exchange membrane, so that the mechanical strength and the dimensional stability of the prepared composite proton exchange membrane are further improved, the condition that the micropores of the base membrane are easily blocked by directly coating sulfonic acid resin solution doped with inorganic particles on the surface of the porous base membrane and the porous structure cannot be densely filled is effectively avoided, and the problem of large swelling degree of the proton exchange membrane in the dry-wet alternating process can be improved;
2) the carbon nanotube double-network structure on the surface of the reinforced composite layer provides more channels for proton conduction, so that the proton conductivity of the composite proton exchange membrane is greatly improved.
Detailed Description
The invention relates to a high proton conductivity enhanced perfluorosulfonic acid composite proton exchange membrane and a preparation method thereof.A porous enhanced membrane is used as an enhanced layer, and firstly, a proper amount of sulfonic acid resin solution is coated on two sides of the porous enhanced membrane; secondly, the sulfonic acid resin mixed solution doped with the sulfonated carbon nanotubes is coated on two sides of the composite membrane, an enhanced network and a proton conduction network of the carbon nanotubes are constructed by regulating and controlling the content of the carbon nanotubes, and the three-layer network composite preparation of the enhanced proton exchange membrane is realized by combining the polymer membrane porous network of the matrix, so that the mechanical strength of the composite proton exchange membrane is obviously improved, and meanwhile, the proton conduction rate of the proton exchange membrane can be effectively improved by doping and modifying the sulfonated carbon nanotubes.
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
The preparation key points of the high-proton conductivity and high-strength perfluorosulfonic acid composite proton exchange membrane in the embodiment are as follows:
(1) coating a perfluorinated sulfonic acid resin solution with the solid content of 15 wt.% on two sides of the porous PTFE membrane through a comma scraper, repeating the coating for 2 times, and drying at 100 ℃ for 10min to obtain a porous PTFE reinforced composite membrane;
(2) emulsifying the sulfonated carbon nano-tubes and a sulfonic acid resin solution at a high speed for 5min, and then performing ultrasonic dispersion for 30min to obtain a perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated multi-walled carbon nano-tubes.
(3) And (3) coating the mixed solution obtained in the step (2) on two sides of the PTFE composite layer obtained in the step (1) through a comma scraper, and drying the solvent to obtain the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength.
(4) The PTFE film used in step (1) had a porosity of 90% and a film thickness of 8 μm.
(5) In the step (2), the length of the multi-wall sulfonated carbon nano-tube is 20 μm, the outer tube diameter is 20nm, the content of S element is 0.2 wt.%, the addition amount of the sulfonated carbon nano-tube is 0.2 wt.% of perfluorosulfonic acid resin, and the solid content of the perfluorosulfonic acid resin is 5 wt.%;
the tensile strength of the composite proton exchange membrane prepared by the embodiment is 58.5MPa, and the proton conductivity at 25 ℃ is 137.1 mS/cm.
Example 2
The preparation key points of the high-proton conductivity and high-strength perfluorosulfonic acid composite proton exchange membrane in the embodiment are as follows:
(1) coating a perfluorinated sulfonic acid resin solution with the solid content of 15 wt.% on two sides of the porous PTFE membrane through a comma scraper, repeating the coating for 2 times, and drying at 100 ℃ for 10min to obtain a porous PTFE reinforced composite membrane;
(2) emulsifying the sulfonated carbon nano-tubes and a sulfonic acid resin solution at a high speed for 5min, and then performing ultrasonic dispersion for 30min to obtain a perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated multi-walled carbon nano-tubes.
(3) And (3) coating the mixed solution obtained in the step (2) on two sides of the PTFE composite layer obtained in the step (1) through a comma scraper, and drying the solvent to obtain the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength.
(4) The PTFE film used in step (1) had a porosity of 90% and a film thickness of 8 μm.
(5) In the step (2), the length of the multi-wall sulfonated carbon nano-tube is 20 μm, the outer tube diameter is 20nm, the content of S element is 0.2 wt.%, the addition amount of the sulfonated carbon nano-tube is 0.1 wt.% of perfluorosulfonic acid resin, and the solid content of the perfluorosulfonic acid resin is 5 wt.%;
the tensile strength of the composite proton exchange membrane prepared by the embodiment is 60MPa, and the proton conductivity at 25 ℃ is 132.0 mS/cm.
Example 3
The preparation key points of the high-proton conductivity and high-strength perfluorosulfonic acid composite proton exchange membrane in the embodiment are as follows:
(1) coating a perfluorinated sulfonic acid resin solution with the solid content of 15 wt.% on two sides of the porous PTFE membrane through a comma scraper, repeating the coating for 2 times, and drying at 100 ℃ for 10min to obtain a porous PTFE reinforced composite membrane;
(2) emulsifying the sulfonated carbon nano-tubes and a sulfonic acid resin solution at a high speed for 5min, and then performing ultrasonic dispersion for 30min to obtain a perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated multi-walled carbon nano-tubes.
(3) And (3) coating the mixed solution obtained in the step (2) on two sides of the PTFE composite layer obtained in the step (1) through a comma scraper, and drying the solvent to obtain the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength.
(4) The PTFE film used in step (1) had a porosity of 90% and a film thickness of 8 μm.
(5) In the step (2), the length of the multi-wall sulfonated carbon nano-tube is 20 μm, the outer tube diameter is 20nm, the content of S element is 0.2 wt.%, the addition amount of the sulfonated carbon nano-tube is 2 wt.% of the perfluorosulfonic acid resin, and the solid content of the perfluorosulfonic acid resin is 5 wt.%;
the tensile strength of the composite proton exchange membrane prepared by the embodiment is 53MPa, and the proton conductivity at 25 ℃ is 124.9 mS/cm.
Example 4
The preparation key points of the high-proton conductivity and high-strength perfluorosulfonic acid composite proton exchange membrane in the embodiment are as follows:
(1) extruding and coating a perfluorinated sulfonic acid resin solution with the solid content of 20 wt.% on two sides of the porous PVDF membrane through a slit, repeating the coating for 2 times, and drying at 100 ℃ for 15min to obtain a porous PVDF reinforced composite membrane;
(2) emulsifying the sulfonated carbon nano tube and the sulfonic acid resin solution at a high speed for 8min, and then performing ultrasonic dispersion for 40min to obtain the perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated single-walled carbon nano tubes.
(3) And (3) coating the mixed solution obtained in the step (2) on two sides of the PVDF composite layer obtained in the step (1) through a comma scraper, and drying the solvent to obtain the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength.
(4) The PVDF film used in step (1) had a porosity of 88% and a film thickness of 10 μm.
(5) The length of the single-wall sulfonated carbon nanotube in the step (2) is 20 microns, the outer tube diameter is 15nm, the S element content is 0.5 wt.%, the addition amount of the sulfonated carbon nanotube is 1 wt.% of the perfluorosulfonic acid resin, and the solid content of the perfluorosulfonic acid resin is 10 wt.%;
the tensile strength of the composite proton exchange membrane prepared by the embodiment is 55MPa, and the proton conductivity at 25 ℃ is 129.6 mS/cm.
Example 5
The preparation key points of the high-proton conductivity and high-strength perfluorosulfonic acid composite proton exchange membrane in the embodiment are as follows:
(1) extruding and coating a perfluorinated sulfonic acid resin solution with the solid content of 8 wt.% on two sides of the porous PE film through a slit, repeating the coating for 3 times, and drying at 50 ℃ for 25min to obtain a porous PE reinforced composite film;
(2) emulsifying the sulfonated carbon nano tube and the sulfonic acid resin solution at a high speed for 3min, and then performing ultrasonic dispersion for 20min to obtain the perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated single-walled carbon nano tubes.
(3) And (3) extruding and coating the mixed solution obtained in the step (2) on two sides of the PE composite layer obtained in the step (1) through a slit, and drying the solvent to obtain the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength.
(4) The PE film used in step (1) had a porosity of 80% and a film thickness of 10 μm.
(5) The length of the single-wall sulfonated carbon nanotube in the step (2) is 20 microns, the outer diameter is 20nm, the content of S element is 0.5 wt.%, the addition amount of the sulfonated carbon nanotube is 2 wt.% of perfluorosulfonic acid resin, and the solid content of the perfluorosulfonic acid resin is 4 wt.%;
the tensile strength of the composite proton exchange membrane prepared by the embodiment is 120MPa, and the proton conductivity at 25 ℃ is 105.0/cm.
Example 6
The preparation key points of the high-proton conductivity and high-strength perfluorosulfonic acid composite proton exchange membrane in the embodiment are as follows:
(1) coating a perfluorinated sulfonic acid resin solution with the solid content of 10 wt.% on two sides of the porous PTFE membrane through a comma scraper, repeating the coating for 3 times, and drying at 80 ℃ for 20min to obtain a porous PTFE reinforced composite membrane;
(2) emulsifying the sulfonated carbon nanotubes and a sulfonic acid resin solution at a high speed for 5min, and then performing ultrasonic dispersion for 10min to obtain a perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated multi-walled carbon nanotubes;
(3) coating the mixed solution obtained in the step (2) on two sides of the PTFE composite layer obtained in the step (1) through a comma scraper, and drying the solvent to obtain the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength;
(4) the PTFE film used in step (1) had a porosity of 85% and a film thickness of 10 μm.
(5) In the step (2), the length of the multi-wall sulfonated carbon nano-tube is 10 μm, the outer tube diameter is 20nm, the content of S element is 0.1 wt.%, the addition amount of the sulfonated carbon nano-tube is 0.1 wt.% of perfluorosulfonic acid resin, and the solid content of the perfluorosulfonic acid resin is 3 wt.%;
the tensile strength of the composite proton exchange membrane prepared by the embodiment is 58MPa, and the proton conductivity at 25 ℃ is 131.2 mS/cm.
Example 7
The preparation key points of the high-proton conductivity and high-strength perfluorosulfonic acid composite proton exchange membrane in the embodiment are as follows:
(1) spraying a perfluorinated sulfonic acid resin solution with the solid content of 2 wt.% on two sides of the porous PTFE membrane, repeating the coating for 2 times, and drying at 30 ℃ for 30min to obtain a porous reinforced composite membrane;
(2) emulsifying the sulfonated carbon nano-tubes and a sulfonic acid resin solution at a high speed for 20min, and then performing ultrasonic dispersion for 60min to obtain a perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated multi-walled carbon nano-tubes.
(3) And (3) spraying the mixed solution obtained in the step (2) on two sides of the PTFE composite layer obtained in the step (1), and drying the solvent to obtain the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength.
(4) The porosity of the porous PTFE film used in step (1) was 80%, and the film thickness was 20 μm.
(5) In the step (2), the length of the multi-wall sulfonated carbon nano-tube is 50 μm, the outer tube diameter is 50nm, the content of S element is 15 wt.%, the addition amount of the sulfonated carbon nano-tube is 10 wt.% of the perfluorosulfonic acid resin, and the solid content of the perfluorosulfonic acid resin solution is 2 wt.%;
the tensile strength of the composite proton exchange membrane prepared by the embodiment is 50MPa, and the proton conductivity at 25 ℃ is 52.6 mS/cm.
Example 8
The preparation key points of the high-proton conductivity and high-strength perfluorosulfonic acid composite proton exchange membrane in the embodiment are as follows:
(1) spraying a perfluorosulfonic acid resin solution with the solid content of 25 wt.% on two sides of the porous PTFE membrane, repeating the coating for 2 times, and drying at 200 ℃ for 10min to obtain a porous reinforced composite membrane;
(2) emulsifying the sulfonated carbon nano-tubes and a sulfonic acid resin solution at a high speed for 1min, and then performing ultrasonic dispersion for 1min to obtain a perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated multi-walled carbon nano-tubes.
(3) And (3) spraying the mixed solution obtained in the step (2) on two sides of the PTFE composite layer obtained in the step (1), and drying the solvent to obtain the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength.
(4) The porosity of the porous PTFE film used in step (1) was 95%, and the film thickness was 2 μm.
(5) In the step (2), the length of the multi-wall sulfonated carbon nano-tube is 5 μm, the outer tube diameter is 5nm, the S element content is 0.05 wt.%, the addition amount of the sulfonated carbon nano-tube is 0.01 wt.% of the perfluorinated sulfonic acid resin, and the solid content of the perfluorinated sulfonic acid resin solution is 20 wt.%;
the tensile strength of the composite proton exchange membrane prepared by the embodiment is 80MPa, and the proton conductivity at 25 ℃ is 137.5 mS/cm.
Example 9
The preparation key points of the high-proton conductivity and high-strength perfluorosulfonic acid composite proton exchange membrane in the embodiment are as follows:
(1) spraying a perfluorosulfonic acid resin solution with the solid content of 25 wt.% on two sides of the porous PTFE membrane, repeating the coating for 4 times, and drying at 150 ℃ for 10min to obtain a porous reinforced composite membrane;
(2) emulsifying the sulfonated carbon nano-tubes and a sulfonic acid resin solution at a high speed for 10min, and then performing ultrasonic dispersion for 25min to obtain a perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated multi-walled carbon nano-tubes.
(3) And (3) spraying the mixed solution obtained in the step (2) on two sides of the PTFE composite layer obtained in the step (1), and drying the solvent to obtain the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength.
(4) The porosity of the porous PTFE film used in step (1) was 95%, and the film thickness was 10 μm.
(5) In the step (2), the length of the multi-wall sulfonated carbon nano-tube is 5 μm, the outer tube diameter is 5nm, the S element content is 0.05 wt.%, the addition amount of the sulfonated carbon nano-tube is 0.01 wt.% of the perfluorinated sulfonic acid resin, and the solid content of the perfluorinated sulfonic acid resin solution is 20 wt.%;
the tensile strength of the composite proton exchange membrane prepared by the embodiment is 60MPa, and the proton conductivity at 25 ℃ is 125.7 mS/cm.
Comparative example 1
The key points of the preparation of the high proton conductivity and high strength perfluorinated sulfonic acid composite proton exchange membrane in the comparative example are as follows:
(1) coating a perfluorinated sulfonic acid resin solution with the solid content of 15 wt.% on two sides of the porous PTFE membrane through a comma scraper, repeating the coating for 2 times, and drying at 100 ℃ for 10min to obtain a porous PTFE reinforced composite membrane;
(2) the porosity of the PTFE film used in the step (1) is 90%, and the thickness of the film is 8 μm;
the tensile strength of the composite proton exchange membrane prepared by the embodiment is 45MPa, and the proton conductivity at 25 ℃ is 110.6 mS/cm.
Comparative example 2
(1) Extruding and coating a perfluorinated sulfonic acid resin solution with the solid content of 20 wt.% on two sides of the porous PVDF membrane through a slit, repeating the coating for 2 times, and drying at 100 ℃ for 15min to obtain a porous PVDF reinforced composite membrane;
(2) the PVDF film used in step (1) had a porosity of 88% and a film thickness of 10 μm.
The tensile strength of the composite proton exchange membrane prepared by the embodiment is 43MPa, and the proton conductivity at 25 ℃ is 108.2 mS/cm.
Comparative example 3
The key points of the preparation of the high proton conductivity and high strength perfluorinated sulfonic acid composite proton exchange membrane in the comparative example are as follows:
(1) extruding and coating a perfluorinated sulfonic acid resin solution with the solid content of 8 wt.% on two sides of the porous PE film through a slit, repeating the coating for 3 times, and drying at 50 ℃ for 25min to obtain a porous PE reinforced composite film;
(2) the PE film used in step (1) had a porosity of 80% and a film thickness of 10 μm.
The tensile strength of the composite proton exchange membrane prepared by the embodiment is 100MPa, and the proton conductivity at 25 ℃ is 94.3 mS/cm.
Comparing example 1 with comparative example 1, it can be seen that the tensile strength of the composite proton exchange membrane coated with the perfluorinated sulfonic acid resin doped with the sulfonated carbon nanotubes is improved by 30%, and the proton conductivity is improved by 24.0%.
Comparing example 2 with comparative example 1, it can be seen that the tensile strength of the composite proton exchange membrane coated with the perfluorinated sulfonic acid resin doped with the sulfonated carbon nanotubes is improved by 33%, and the proton conductivity is improved by 19.3%.
Comparing example 3 with comparative example 1, it can be seen that the tensile strength of the composite proton exchange membrane coated with the perfluorinated sulfonic acid resin doped with the sulfonated carbon nanotube is improved by 17.8%, and the proton conductivity is improved by 12.9%.
Comparing example 4 with comparative example 2, it can be seen that the tensile strength of the composite proton exchange membrane coated with the perfluorinated sulfonic acid resin doped with the sulfonated carbon nanotube is improved by 27.9%, and the proton conductivity is improved by 19.7%.
Comparing example 5 with comparative example 3, it can be seen that the tensile strength of the composite proton exchange membrane coated with the perfluorinated sulfonic acid resin doped with the sulfonated carbon nanotube is improved by 20%, and the proton conductivity is improved by 11.3%.
The results show that the composite proton exchange membrane coated with the sulfonated carbon nanotube-doped perfluorosulfonic acid resin can realize the construction of a three-layer network structure in a matrix, so that the network structure plays a role in enhancing and obviously improving the mechanical strength of the composite proton exchange membrane, and the proton transmission network structure is formed to effectively improve the proton conductivity of the proton exchange membrane.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength is characterized by comprising the following steps:
s1: coating the perfluorinated sulfonic acid resin solution on two sides of the porous enhancement layer in a solution casting manner, repeating for 2-4 times, and drying the solvent to obtain an enhanced composite membrane;
s2: fully emulsifying the sulfonated carbon nanotubes and a perfluorinated sulfonic acid resin solution, and then carrying out ultrasonic mixing to obtain a perfluorinated sulfonic acid resin solution with uniformly dispersed sulfonated carbon nanotubes;
s3: and (3) coating the perfluorinated sulfonic acid resin solution with the uniformly dispersed sulfonated carbon nanotubes obtained in the step (S2) on two sides of the reinforced composite membrane in a solution casting manner, and drying the solvent to obtain the perfluorinated sulfonic acid composite proton exchange membrane with high proton conductivity and high strength.
2. The method for preparing a perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength according to claim 1, wherein the porous reinforcing layer material in S1 is one or a combination of polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone and polyethylene.
3. The preparation method of the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength according to claim 2, wherein the porosity of the porous reinforcement layer in S1 is 80-95%, and the thickness is 2-20 μm.
4. The preparation method of the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength according to claim 1, wherein the solvent in the perfluorosulfonic acid resin solution in S1 and S2 is a mixed solvent of one or more of n-propanol, water, ethanol and dimethyl sulfoxide, wherein the solid content of the perfluorosulfonic acid resin solution is 2-25 wt.%.
5. The method for preparing the perfluorinated sulfonic acid composite proton exchange membrane with high proton conductivity and high strength according to claim 1, wherein the sulfonated carbon nanotube in S2 is a single-walled or multi-walled carbon nanotube, the sulfonated carbon nanotube has a length of 5-50 μm and a tube diameter of 5-50 nm, and the content of S element in the sulfonated carbon nanotube is 0.05-15 wt.%.
6. The method for preparing the perfluorinated sulfonic acid composite proton exchange membrane with high proton conductivity and high strength according to claim 1, wherein the addition amount of the sulfonated carbon nanotubes in the sulfonated carbon nanotube doped layer in S2 is 0.01 to 10 wt% of the mass of the perfluorinated sulfonic acid resin.
7. The preparation method of the perfluorinated sulfonic acid composite proton exchange membrane with high proton conductivity and high strength according to claim 6, wherein in S3, a carbon nanotube enhanced network and a proton conduction network are constructed on the surface of the enhanced composite membrane through a perfluorinated sulfonic acid resin solution in which sulfonated carbon nanotubes are uniformly dispersed, and the enhanced proton exchange membrane is prepared by three-layer network composite by combining a polymer membrane porous network of the enhanced composite membrane matrix.
8. The preparation method of the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity and high strength according to claim 1, wherein the emulsification process comprises the following steps: emulsifying at high speed for 1-20 min by using an emulsifying machine;
the ultrasonic time is 1-60 min;
the drying temperature in S1 and S3 is 30-200 ℃, and the drying time is 10-30 min.
9. The method for preparing the perfluorosulfonic acid composite proton exchange membrane with high proton conductivity according to claim 1, wherein the solution casting method in S1 and S3 comprises the following steps: adopting one or more of knife coating, slit extrusion, comma scraper, dip coating, spray coating and the like.
10. The perfluorinated sulfonic acid composite proton exchange membrane with high proton conductivity and high strength prepared by the preparation method of any one of claims 1 to 9, wherein the thickness of the composite proton exchange membrane is 5-30 μm.
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