CN114665134A - Proton exchange membrane and preparation method and application thereof - Google Patents
Proton exchange membrane and preparation method and application thereof Download PDFInfo
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- CN114665134A CN114665134A CN202210320363.8A CN202210320363A CN114665134A CN 114665134 A CN114665134 A CN 114665134A CN 202210320363 A CN202210320363 A CN 202210320363A CN 114665134 A CN114665134 A CN 114665134A
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- 239000012528 membrane Substances 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 78
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 76
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 76
- 239000002131 composite material Substances 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 34
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 11
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000003490 calendering Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000002525 ultrasonication Methods 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 23
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 14
- 239000010408 film Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 229910000420 cerium oxide Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000012028 Fenton's reagent Substances 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000004706 metal oxides Chemical group 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water 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
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
-
- 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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- 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
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
Abstract
The invention relates to a proton exchange membrane and a preparation method and application thereof, wherein the proton exchange membrane comprises a first perfluorinated sulfonic acid resin membrane, a polytetrafluoroethylene composite membrane and a second perfluorinated sulfonic acid resin membrane which are sequentially stacked; the polytetrafluoroethylene composite membrane comprises polytetrafluoroethylene and cerium dioxide. According to the invention, through the fixation of the polytetrafluoroethylene resin, cerium dioxide nano particles stably exist in the proton exchange membrane, so that the durability of the proton exchange membrane is improved in the operation process of the battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a proton exchange membrane and a preparation method and application thereof.
Background
The hydrogen fuel cell core component Membrane Electrode (MEA) mainly comprises a catalyst, a proton exchange membrane and a gas diffusion layer. Wherein, the proton exchange membrane is used as the middle layer of the MEA and has the functions of gas resistance and mass transfer. At present, the mainstream products in the market mainly adopt a composite proton exchange membrane developed by Goll company, and mainly comprise a perfluorinated sulfonic acid resin solution (PFSA) which mainly conducts protons to form a conductive effect; the ePTFE microporous membrane with a net structure mainly has a supporting and reinforcing effect.
CN109560310A discloses a method for preparing an ultralow platinum loading self-humidifying membrane electrode of a proton exchange membrane fuel cell, wherein the prepared membrane electrode is prepared by attaching a substance with a moisturizing effect on a carbon carrier in the form of a thin film, uniformly mixing and ultrasonically treating the substance, preparing an anode substrate catalyst layer on one side of a proton exchange membrane by using a spraying technology to serve as a moisturizing layer, and then carrying a nano platinum catalyst with a hydrogen catalysis function on the substrate catalyst layer by using a pulse electrodeposition technology. The moisture-keeping layer is a metal oxide and non-metal oxide film. The nanometer platinum catalyst is used as an active component and is dispersed on the surface of the oxide. The disclosed coating of the metal oxide or non-metal oxide film can simultaneously improve the hydrophilicity and water-retaining property of the basal layer, effectively improve the dispersibility of noble metal platinum in the pulse electrodeposition process, and enable the platinum nanoparticles to establish stronger interaction with the basal oxide, thereby greatly improving the stability of the noble metal catalyst.
CN109037555A discloses a lithium ion battery separator, comprising: a porous substrate and a polymer coating layer coated on at least one side surface of the porous substrate; the polymer material comprises at least one of the group consisting of polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polyethyl acrylate, polyacrylic acid-styrene copolymer, neopentyl glycol diacrylate, polytetrafluoroethylene, polyimide, polyamides, polyesters, polysulfones, and polyacrylonitrile. The disclosed polymer has good bonding property, and the prepared polymer coating is thin, uniform and continuously distributed, so that the bonding property between the polymer coating and a porous base material, between the polymer coating and positive and negative pole pieces can be improved, and the hardness of a battery core is further improved; in addition, a large number of micropores are formed among the polymer particles, and meanwhile, the polymer particles are less swelled in the electrolyte, so that the obtained separation membrane has good air permeability and good battery cyclicity.
However, during the operation of the fuel cell, the generated chemical reaction can generate free radicals to attack the C-F, C-C, C-O bond of the proton exchange membrane, so that the proton exchange membrane is gradually decomposed to cause cracks.
In view of the above, it is important to develop a proton exchange membrane having excellent durability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a proton exchange membrane and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a proton exchange membrane comprising a first perfluorosulfonic acid resin membrane, a polytetrafluoroethylene composite membrane, and a second perfluorosulfonic acid resin membrane, which are sequentially stacked;
the polytetrafluoroethylene composite membrane comprises polytetrafluoroethylene and cerium dioxide.
In the invention, the cerium dioxide in the proton exchange membrane is used as a free radical quencher and exists in the polytetrafluoroethylene composite membrane, and is fixed by polytetrafluoroethylene so as to stably exist in the proton exchange membrane. When the proton exchange membrane is used in a fuel cell, the phenomenon that the acting force of cerium dioxide and perfluorinated sulfonic acid resin (PFSA) is relatively weak due to the fact that the cerium dioxide and the PFSA are mixed in a physical blending mode is avoided, the phenomenon that the cerium dioxide is lost due to the water transportation effect is avoided, and particularly the phenomenon that the cerium dioxide is lost seriously due to the fact that humidity is greatly changed under the start-stop working condition of a pile is avoided.
In the prior art, the proton exchange membrane is prepared by casting and coating PFSA mixed with nano particles on the surface of an ePTFE microporous membrane, and PFSA solution in the middle layer is partially replaced, so that the nano particles are in a non-uniform distribution state. According to the invention, cerium dioxide nanoparticles are introduced into the tetrafluoroethylene composite membrane, so that the distribution uniformity of the proton exchange membrane filler is effectively improved.
Preferably, the ceria has a particle size of 5-20nm, e.g., 6nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, etc.
In the invention, the particle size of the cerium dioxide is 5-20nm, and the particle size is too large, so that the formed proton exchange membrane is easy to generate defects of mechanical property; the particle size is too small, the cerium dioxide is easy to agglomerate and is not easy to be uniformly dispersed, and the performance of the formed proton exchange membrane is poor.
Preferably, the polytetrafluoroethylene composite membrane also comprises a water retention agent and/or a quenching agent.
Preferably, the water retaining agent comprises silicon dioxide and/or zirconium dioxide.
Preferably, the mass percentage of the cerium oxide is 0.1% to 50%, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc., based on 100% of the total mass of the polytetrafluoroethylene.
In the invention, the reason for controlling the mass percent of the cerium dioxide to be 0.1-50% is that the compatibility between the inorganic filler and the organic polymer is poor, and the ratio of the cerium dioxide is too high, so that the proton exchange membrane can not form a membrane; the content of cerium dioxide is too low, and the quenching effect of free radicals is not obvious.
Preferably, the polytetrafluoroethylene composite film further includes a lubricant.
Preferably, the lubricant comprises an isoparaffinic compound, such as any one of Mobil Isopar M, Mobil Isopar G, or Mobil Isopar H, or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of Mobil Isopar M and Mobil Isopar G, a combination of Mobil Isopar G and Mobil Isopar H, a combination of Mobil Isopar M, Mobil Isopar G and Mobil Isopar H, etc., and Mobil Isopar M is more preferable.
In the invention, the lubricant is preferably an isoparaffin compound, and is further preferably Mobil Isopar M, and the lubricant can be used not only as a processing aid of polytetrafluoroethylene, but also as a solvent of cerium dioxide, so that the dispersion of the cerium dioxide in the polytetrafluoroethylene is facilitated.
Preferably, the lubricant is present in an amount of 20% to 30%, such as 22%, 24%, 26%, 28%, etc., based on 100% of the total mass of the polytetrafluoroethylene.
In the present invention, the reason why the mass percentage of the lubricant is controlled to be in this range is that this range can achieve both the dispersion of ceria and the processing of polytetrafluoroethylene.
Preferably, the thickness ratio of the first perfluorosulfonic acid resin film, the polytetrafluoroethylene composite film and the second perfluorosulfonic acid resin film is 1: (1.1-2): (0.8-1.2), wherein 1.1-2 can be 1.2, 1.4, 1.6, 1.8, etc., and 0.8-1.2 can be 0.9, 1.0, 1.1, etc.
Preferably, the thickness of the polytetrafluoroethylene composite membrane is 9 to 11 μm, such as 9.5 μm, 10 μm, 10.5 μm, and the like.
Preferably, the polytetrafluoroethylene composite membrane has a porosity of 80% to 90%, such as 82%, 84%, 86%, 88%, and the like.
Preferably, the transverse and longitudinal strength of the polytetrafluoroethylene composite membrane is more than or equal to 30MPa, such as 32MPa, 34MPa, 36MPa, 38MPa, 40MPa and the like.
Preferably, the gram weight of the polytetrafluoroethylene composite membrane is 3-5g/m2For example 3.2g/m2、3.4g/m2、3.6g/m2、3.8g/m2、4g/m2、4.2g/m2、4.4g/m2、4.6g/m2、4.8g/m2And the like.
In a second aspect, the present invention provides a method for preparing the proton exchange membrane of the first aspect, the method comprising the following steps:
(1) mixing polytetrafluoroethylene with cerium dioxide, and processing to obtain a polytetrafluoroethylene composite membrane;
(2) and (2) coating a perfluorinated sulfonic acid resin solution on the surface of the polytetrafluoroethylene composite membrane in the step (1), and curing to form a perfluorinated sulfonic acid resin membrane to obtain the proton exchange membrane.
According to the preparation method, cerium dioxide nano particles are directly mixed into the proton exchange membrane in the material mixing process in the preparation link of the polytetrafluoroethylene composite membrane, so that the stability of the nano particles is greatly improved, and the durability of the proton exchange membrane is improved.
Preferably, in the step (1), the mixing manner includes stirring and ultrasound.
Preferably, the stirring time is 30-60min, such as 35min, 40min, 45min, 50min, 55min, and the like.
Preferably, the time of the ultrasound is 30-60min, such as 35min, 40min, 45min, 50min, 55min, and the like.
Preferably, the processing means include curing, blanking, extrusion, calendering, degreasing, longitudinal stretching and transverse stretching.
Preferably, the cerium oxide is prepared as a cerium oxide solution before the polytetrafluoroethylene is mixed.
Preferably, the solvent in the ceria solution comprises an isoparaffin compound, for example any one of Mobil Isopar M, Mobil Isopar G or Mobil Isopar H, or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of Mobil Isopar M and Mobil Isopar G, a combination of Mobil Isopar G and Mobil Isopar H, a combination of Mobil Isopar M, Mobil Isopar G and Mobil Isopar H, etc., and Mobil Isopar M is more preferable.
Preferably, the ceria solution has a mass concentration of 0.1% to 10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc., and more preferably 0.5% to 2%.
Preferably, in the step (2), the coating manner includes casting.
Preferably, in the step (2), the curing includes a first curing and a second curing.
Preferably, the temperature of the first curing is 80-100 ℃, such as 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃ and the like.
Preferably, the time for the first curing is 1-2h, such as 1.2h, 1.4h, 1.6h, 1.8h, etc.
Preferably, the temperature of the second curing is 110-.
Preferably, the time for the second curing is 1-2h, such as 1.2h, 1.4h, 1.6h, 1.8h, and the like.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) stirring polytetrafluoroethylene and cerium dioxide for 30-60min, performing ultrasonic treatment for 30-60min, sequentially performing curing, blank making, extrusion, calendaring, deoiling, longitudinal stretching and transverse stretching to obtain a polytetrafluoroethylene composite membrane;
(2) coating a perfluorinated sulfonic acid resin solution on the surface of the polytetrafluoroethylene composite membrane in the step (1), firstly curing for 1-2h at the temperature of 80-100 ℃, and then curing for 1-2h at the temperature of 110-130 ℃ for the second time to form a perfluorinated sulfonic acid resin membrane, thereby obtaining the proton exchange membrane.
In a third aspect, the present invention provides a hydrogen fuel cell comprising the proton exchange membrane of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, through the fixation of the polytetrafluoroethylene resin, cerium dioxide nano particles stably exist in the proton exchange membrane, so that the durability of the proton exchange membrane is improved in the operation process of the battery.
(2) After the proton exchange membrane is soaked in Fenton reagent for 72 hours, the content of fluorine ions is between 8 and 13Mg F-/g nafion, the damage degree of the proton exchange membrane is low, and the durability is excellent; in the mechanical property test, the tensile strength in the TD direction is 18-32.2Mpa, the tensile strength in the MD direction is 17-34.4Mpa, and the mechanical property is better.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The raw materials and information of the embodiments of the invention are as follows:
polytetrafluoroethylene: PTFE, available from DuPont under the trade designation 601X, having a crystallinity of 98% or more, and a standard specific gravity SSG of 2.149 (typically measured in water, i.e., weight in water, to indicate the molecular weight of the high molecular weight resin);
lubricant/solvent: isomeric hexadecane, Mobil Isopar M;
cerium oxide: CeO (CeO)2Purchased from Sigma, particle size between 5 and 20 nm;
perfluorosulfonic acid resin solution: available from kemu chemistry under the trade designation nafion D2021s, 20% solids content, ion exchange capacity IEC: 0.95-1.03.
Example 1
The present embodiment provides a proton exchange membrane, which includes a first perfluorosulfonic acid resin membrane, a polytetrafluoroethylene composite membrane, and a second perfluorosulfonic acid resin membrane, which are sequentially stacked, and a thickness ratio of the first perfluorosulfonic acid resin membrane to the second perfluorosulfonic acid resin membrane is 3:4: 3;
the polytetrafluoroethylene composite membrane comprises polytetrafluoroethylene and cerium dioxide (the particle size is 5 nm).
The preparation method of the proton exchange membrane comprises the following steps:
(1) 200mL (about 155.6g) of Isopar M adjuvant was added to a 500mL beaker and 1.556g of CeO was weighed2Mixing the nano particles with Isopar M auxiliary agent to form an auxiliary agent solution (the content is 1 wt%), stirring for 60min, performing ultrasonic treatment for 30min, transferring the mixed solution to 622.4g of PTFE resin, mixing for 30min by using a custom mixer, curing, blank making, extruding, calendaring, deoiling, longitudinally stretching and transversely stretching to obtain the polytetrafluoroethylene composite film;
the thickness of the polytetrafluoroethylene composite membrane is 10 mu m, the porosity is 85 percent, the transverse and longitudinal strength is 30Mpa, and the gram weight is 3.5g/m2；
(2) Cutting a 10 x 10cm polytetrafluoroethylene composite membrane, coating a perfluorinated sulfonic acid resin solution into a membrane in a solution casting manner, drying at 80 ℃ for 12 hours to remove a solvent, curing at 100 ℃ for 2 hours in a vacuum oven, and curing at 120 ℃ for 2 hours to obtain the proton exchange membrane.
Example 2
The present embodiment provides a proton exchange membrane, which includes a first perfluorosulfonic acid resin membrane, a polytetrafluoroethylene composite membrane, and a second perfluorosulfonic acid resin membrane, which are sequentially stacked, and a thickness ratio of the first perfluorosulfonic acid resin membrane to the second perfluorosulfonic acid resin membrane is 3:4: 3;
the polytetrafluoroethylene composite membrane comprises polytetrafluoroethylene and cerium dioxide (the particle size is 10 nm).
The preparation method of the proton exchange membrane comprises the following steps:
(1) 200mL (about 155.6g) of Isopar M adjuvant was added to a 500mL beaker and 1.556g of CeO was weighed2Mixing the nano particles with Isopar M auxiliary agent to form an auxiliary agent solution (the content is 1 wt%), stirring for 60min, performing ultrasonic treatment for 30min, transferring the mixed solution to 622.4g of PTFE resin, mixing for 30min by using a custom mixer, curing, blank making, extruding, calendaring, deoiling, longitudinally stretching and transversely stretching to obtain the polytetrafluoroethylene composite film;
the thickness of the polytetrafluoroethylene composite membrane is 10 mu m, the porosity is 85 percent, the transverse and longitudinal strength is 30Mpa, and the gram weight is 3.5g/m2；
(2) Cutting a 10 x 10cm polytetrafluoroethylene composite membrane, coating a perfluorinated sulfonic acid resin solution into a membrane in a solution casting manner, drying at 80 ℃ for 12 hours to remove a solvent, curing at 100 ℃ for 2 hours in a vacuum oven, and curing at 120 ℃ for 2 hours to obtain the proton exchange membrane.
Example 3
The present embodiment provides a proton exchange membrane, which includes a first perfluorosulfonic acid resin membrane, a polytetrafluoroethylene composite membrane, and a second perfluorosulfonic acid resin membrane, which are sequentially stacked, and a thickness ratio of the first perfluorosulfonic acid resin membrane to the second perfluorosulfonic acid resin membrane is 3:4: 3;
the polytetrafluoroethylene composite membrane comprises polytetrafluoroethylene and cerium dioxide (the particle size is 10 nm).
The preparation method of the proton exchange membrane comprises the following steps:
(1) 200mL (about 155.6g) of Isopar M adjuvant was added to a 500mL beaker and 1.556g of CeO was weighed2Mixing the nano particles with Isopar M auxiliary agent to form an auxiliary agent solution (the content is 1 wt%), stirring for 60min, performing ultrasonic treatment for 30min, transferring the mixed solution into 622.4g of PTFE resin, mixing for 30min by using a customized mixer, and performing curing, blank making, extrusion, calendering, deoiling, longitudinal stretching and transverse stretching to obtain the polytetrafluoroethylene composite film;
the thickness of the polytetrafluoroethylene composite membrane is 10 mu m, the porosity is 85 percent, the transverse and longitudinal strength is 30Mpa, and the gram weight is 3.5g/m2
(2) Cutting a 10 x 10cm polytetrafluoroethylene composite membrane, coating a perfluorinated sulfonic acid resin solution into a membrane in a solution casting manner, drying at 80 ℃ for 12 hours to remove a solvent, curing at 100 ℃ for 2 hours in a vacuum oven, and curing at 120 ℃ for 2 hours to obtain the proton exchange membrane.
Example 4
This example is different from example 1 in that the mass of cerium oxide was 0.1556g (0.1% by weight in the assistant solution), and the rest was the same as example 1.
Example 5
This example is different from example 1 in that the mass of ceria was 15.56g (10% wt in the assistant solution), and the rest was the same as example 1.
Comparative example 1
This comparative example is different from example 1 in that cerium oxide is not included, and the rest is the same as example 1.
Comparative example 2
The proton exchange membrane comprises a first perfluorinated sulfonic acid resin membrane, a polytetrafluoroethylene composite membrane and a second perfluorinated sulfonic acid resin membrane which are sequentially stacked, wherein the thickness ratio of the first perfluorinated sulfonic acid resin membrane to the second perfluorinated sulfonic acid resin membrane is 3:4: 3.
The preparation method of the proton exchange membrane comprises the following steps:
(1) adding 200mL (about 155.6g) of Isopar M auxiliary agent into 622.4g of PTFE resin in a 500mL beaker, mixing for 30min by using a customized mixer, and then performing curing, blank making, extrusion, calendaring, deoiling, longitudinal stretching and transverse stretching to obtain the polytetrafluoroethylene composite membrane;
(2) cutting 10 × 10cm polytetrafluoroethylene composite membrane to obtain a composite membrane containing 1.556g of CeO2Coating the nanoparticle perfluorosulfonic acid resin solution into a film by solution casting, drying at 80 deg.C for 12h to remove solvent, curing at 100 deg.C for 2h in a vacuum oven, and curing at 120 deg.C for 2h to obtain the final productTo the proton exchange membrane.
Performance testing
The proton exchange membranes described in examples 1-5 and comparative examples 1-2 were tested as follows:
(1) content of fluorine ions: detecting the content of fluorine ions by a Fenton reagent to judge the damage degree of the proton membrane;
1) 25mg of FeSO are weighed4·7H2Dissolving and dispersing O into 100mL of ultrapure water, dropwise adding nitric acid, and adjusting the pH to 3; 20mL of the above solution was weighed, transferred to a 1L volumetric flask, and 500mL of H was sequentially added2O and 100mL H2O2Then, fixing the volume to 1L to obtain a Fenton reagent;
2) cutting a proton exchange membrane by 5 multiplied by 5cm, placing the proton exchange membrane in a culture dish, adding a quantitative Fenton reagent, uniformly soaking for 72 hours, and testing the content of the fluoride ions, wherein the unit is Mg F-/g nafion, which represents the mass of the fluoride ions separated out from each gram of proton exchange membrane, and the separated out amount is measured in Mg.
(2) And (3) mechanical testing: the mechanical properties, mainly tensile strength, of the proton exchange membrane are evaluated by detection.
1) The sample should be under the conditions of constant temperature and constant humidity, temperature: 25 ℃ ± 2 ℃, humidity: standing for 10h at 50% +/-5%;
2) under the condition, the average thickness d of the sample is measured, the thickness measurement accuracy is +/-0.2%, and the width measurement accuracy is +/-0.5%;
3) correcting a zero point before testing, placing a sample on a starting clamp, overlapping the upper center and the lower center, and selecting a pneumatic clamp with a pressure value of 0.4 MPa; the tensile speed of the tester is 50mm/min, and the corresponding load value is read after the test piece is broken.
The test results are summarized in table 1.
TABLE 1
The data in the table 1 are analyzed, so that the content of fluorine ions in the proton exchange membrane is between 8 and 13Mg F-/g nafion after the proton exchange membrane is soaked in a Fenton reagent for 72 hours, the damage degree of the proton exchange membrane is low, and the durability is excellent; in the mechanical property test, the tensile strength in the TD direction is 18-32.2Mpa, the tensile strength in the MD direction is 17-34.4Mpa, and the mechanical property is better.
As can be seen from the analysis of comparative example 1 and example 1, the content of fluorine ions in comparative example 1 is significantly higher than that in example 1, which proves that the proton exchange membrane formed by adding cerium oxide has better performance.
As can be seen from the analysis of comparative example 2 and example 1, comparative example 2 is inferior in performance to example 1, and it is demonstrated that the formed proton exchange membrane has better performance by immobilizing cerium oxide in the polytetrafluoroethylene composite membrane.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The proton exchange membrane is characterized by comprising a first perfluorinated sulfonic acid resin membrane, a polytetrafluoroethylene composite membrane and a second perfluorinated sulfonic acid resin membrane which are sequentially stacked;
the polytetrafluoroethylene composite membrane comprises polytetrafluoroethylene and cerium dioxide.
2. The proton exchange membrane according to claim 1, wherein the ceria has a particle size of 5-20 nm.
3. The proton exchange membrane according to claim 1 or 2, wherein the mass percent of the cerium dioxide is 0.1% -50% based on 100% of the total mass of the polytetrafluoroethylene;
preferably, the polytetrafluoroethylene composite film further comprises a lubricant;
preferably, the lubricant comprises an isoparaffinic compound;
preferably, the mass percent of the lubricant is 20-30% based on the total mass of the polytetrafluoroethylene being 100%.
4. The proton exchange membrane according to any one of claims 1 to 3, wherein the thickness ratio of the first perfluorosulfonic acid resin membrane, the polytetrafluoroethylene composite membrane and the second perfluorosulfonic acid resin membrane is 1: (1.1-2): (0.8-1.2).
5. The proton exchange membrane according to any one of claims 1 to 4, wherein the polytetrafluoroethylene composite membrane has a thickness of 9 to 11 μm;
preferably, the porosity of the polytetrafluoroethylene composite membrane is 80% -90%.
6. The proton exchange membrane according to any one of claims 1 to 5, wherein the transverse and longitudinal strength of the polytetrafluoroethylene composite membrane is greater than or equal to 30 MPa;
preferably, the gram weight of the polytetrafluoroethylene composite membrane is 3-5g/m2。
7. A method for preparing a proton exchange membrane according to any one of claims 1 to 6, wherein the method comprises the following steps:
(1) mixing polytetrafluoroethylene with cerium dioxide, and processing to obtain a polytetrafluoroethylene composite membrane;
(2) and (2) coating a perfluorinated sulfonic acid resin solution on the surface of the polytetrafluoroethylene composite membrane in the step (1), and curing to form a perfluorinated sulfonic acid resin membrane to obtain the proton exchange membrane.
8. The method according to claim 7, wherein in the step (1), the mixing means includes stirring and ultrasonication;
preferably, the stirring time is 30-60 min;
preferably, the time of the ultrasonic treatment is 30-60 min;
preferably, the processing modes comprise curing, blank making, extrusion, calendering, deoiling, longitudinal stretching and transverse stretching;
preferably, in the step (2), the curing includes a first curing and a second curing;
preferably, the temperature of the first curing is 80-100 ℃;
preferably, the time for the first curing is 1-2 h;
preferably, the temperature of the second curing is 110-;
preferably, the time of the second curing is 1 to 2 hours.
9. The method according to claim 7 or 8, characterized in that it comprises the steps of:
(1) stirring polytetrafluoroethylene and cerium dioxide for 30-60min, performing ultrasonic treatment for 30-60min, sequentially performing curing, blank making, extrusion, calendering, deoiling, longitudinal stretching and transverse stretching to obtain a polytetrafluoroethylene composite film;
(2) coating a perfluorinated sulfonic acid resin solution on the surface of the polytetrafluoroethylene composite membrane in the step (1), firstly curing for 1-2h at 80-100 ℃, and then curing for 1-2h at 110-130 ℃ for the second time to form a perfluorinated sulfonic acid resin membrane, thereby obtaining the proton exchange membrane.
10. A hydrogen fuel cell comprising the proton exchange membrane according to any one of claims 1 to 6.
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