CN115084608A - Oxidation-resistant proton exchange membrane, preparation method thereof and proton exchange membrane fuel cell - Google Patents
Oxidation-resistant proton exchange membrane, preparation method thereof and proton exchange membrane fuel cell Download PDFInfo
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- CN115084608A CN115084608A CN202210696054.0A CN202210696054A CN115084608A CN 115084608 A CN115084608 A CN 115084608A CN 202210696054 A CN202210696054 A CN 202210696054A CN 115084608 A CN115084608 A CN 115084608A
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- exchange membrane
- proton exchange
- conductive polymer
- acid solution
- radical scavenger
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- 239000000446 fuel Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 238000007254 oxidation reaction Methods 0.000 title claims description 8
- 239000000243 solution Substances 0.000 claims abstract description 87
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 75
- 239000002516 radical scavenger Substances 0.000 claims abstract description 53
- 239000002105 nanoparticle Substances 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 47
- 229940123457 Free radical scavenger Drugs 0.000 claims abstract description 43
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 33
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
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- 238000002156 mixing Methods 0.000 claims abstract description 10
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 125000001041 indolyl group Chemical group 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 8
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- 238000004220 aggregation Methods 0.000 abstract description 3
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- 239000010410 layer Substances 0.000 description 36
- 150000003254 radicals Chemical class 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000002791 soaking Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229920000767 polyaniline Polymers 0.000 description 11
- 229920000128 polypyrrole Polymers 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
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- 239000002344 surface layer Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
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- 229910052684 Cerium Inorganic materials 0.000 description 4
- -1 cerium ions Chemical class 0.000 description 4
- 230000007760 free radical scavenging Effects 0.000 description 4
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- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
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- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
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- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- LFDGRWDETVOGDT-UHFFFAOYSA-N 1h-pyrrole;hydrochloride Chemical compound Cl.C=1C=CNC=1 LFDGRWDETVOGDT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
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- 230000005684 electric field Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000002292 Radical scavenging effect Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical group [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Images
Classifications
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- 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
- H01M8/1069—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
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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 provides a preparation method of an antioxidant proton exchange membrane, which comprises the following steps: A) adding an oxidant and free radical scavenger nanoparticles into an acid solution to obtain an oxidant solution; the free radical scavenger nanoparticles are cerium oxide nanoparticles and/or manganese oxide nanoparticles; B) uniformly mixing an oxidant solution and an acid solution of a conductive polymer monomer to obtain a mixed solution; C) and adding the mixed solution to one side of the proton exchange membrane, and carrying out in-situ growth to form a conductive polymer layer containing the free radical scavenger nanoparticles so as to obtain the antioxidant proton exchange membrane. The proton exchange membrane is used as a basic membrane layer, the conductive polymer grows on the surface of the membrane in situ, the free radical scavenger particles are wrapped, the particle aggregation is prevented, the loss of the free radical scavenger is relieved, the service life of the free radical scavenger is prolonged, and the stability of the fuel cell is improved. The invention also provides an anti-oxidation proton exchange membrane and a proton exchange membrane fuel cell.
Description
Technical Field
The invention belongs to the technical field of proton exchange membranes, and particularly relates to an antioxidant proton exchange membrane, a preparation method thereof and a proton exchange membrane fuel cell.
Background
Proton Exchange Membrane Fuel Cell (PEMFC) is a device which takes hydrogen as fuel and converts chemical energy into electric energy, wherein the proton exchange membrane is the core unit of the PEMFC, conducts protons to form a cell loop and can separate the anode and cathode of the PEMFC, so the conductivity and stability of the PEMFC are very important.
During the operation of the fuel cell, the incomplete reaction of oxygen and proton on the cathode side generates hydrogen peroxide, further reaction of the hydrogen peroxide generates hydroxyl radical and hydrogen peroxide radical, hydrogen gas on the anode side forms hydrogen radical on the surface of the catalyst layer, the hydrogen radical reacts with oxygen permeated from the cathode side to generate hydrogen peroxide radical, part of the hydrogen peroxide radical reacts with hydrogen ion to generate hydrogen peroxide, and further the same reaction as that on the anode side generates hydroxyl radical and hydrogen peroxide radical.
The conventional proton exchange membrane is easy to be attacked by free radicals due to the existence of ether bonds, carbon-sulfur bonds, benzene rings and other structures in the structure, so that the degradation of a polymer chain is caused, the stability of the proton exchange membrane is reduced, and the performance of a fuel cell is unstable.
Disclosure of Invention
The invention aims to provide an anti-oxidation proton exchange membrane, a preparation method thereof and a proton exchange membrane fuel cell.
The invention provides a preparation method of an antioxidant proton exchange membrane, which comprises the following steps:
A) adding an oxidant and free radical scavenger nanoparticles into an acid solution to obtain an oxidant mixed solution;
the free radical scavenger nanoparticles are cerium oxide nanoparticles and/or manganese oxide nanoparticles;
B) uniformly mixing the oxidant mixed solution with the acid solution of the conductive polymer monomer to obtain a mixed solution;
C) and respectively adding the mixed solution and an acid solution with the same acid concentration as the mixed solution to the two sides of the proton exchange membrane, and carrying out in-situ growth to form a conductive polymer layer containing the free radical scavenger nanoparticles so as to obtain the antioxidant proton exchange membrane.
Preferably, the conductive polymer monomer includes aniline and/or pyrrole;
in the acid solution of the conductive polymer monomer, the concentration of the conductive polymer monomer is 0.05-0.5 mol/L.
Preferably, the acid solution of the conductive polymer monomer is prepared by mixing the conductive polymer monomer and the acid solution;
the acid solution is a hydrochloric acid solution or a sulfuric acid solution, and the concentration of the acid solution is 0.5-5 mol/L.
Preferably, the oxidant is ammonium persulfate and/or ferric trichloride;
the molar ratio of the oxidant to the conductive polymer monomer is 1: (1-4).
Preferably, the molar ratio of the radical scavenger nanoparticles to the conductive polymer monomer is 1: (1-2).
Preferably, the in-situ growth temperature is 2-8 ℃; the in-situ growth time is 1-10 hours.
Preferably, the proton exchange membrane is a perfluorosulfonic acid proton exchange membrane or a sulfonated polybiphenyl indole proton exchange membrane.
The invention provides an antioxidant proton exchange membrane prepared by the preparation method, which comprises a proton exchange membrane and a conductive polymer layer growing on the surface of the proton exchange membrane in situ;
the conductive polymer layer includes a conductive polymer and a radical scavenger nanoparticle encapsulated within the conductive polymer.
Preferably, the thickness of the conductive polymer layer is 400 to 500 nm.
The invention provides a proton exchange membrane fuel cell, which comprises the antioxidant proton exchange membrane.
The invention provides a preparation method of an antioxidant proton exchange membrane, which comprises the following steps: A) adding an oxidant and free radical scavenger nanoparticles into an acid solution to obtain an oxidant solution; the free radical scavenger nanoparticles are cerium oxide nanoparticles and/or manganese oxide nanoparticles; B) uniformly mixing an oxidant solution and an acid solution of a conductive polymer monomer to obtain a mixed solution; C) and adding the mixed solution to one side of the proton exchange membrane, and carrying out in-situ growth to form a conductive polymer layer containing the free radical scavenger nanoparticles so as to obtain the antioxidant proton exchange membrane. The proton exchange membrane is used as a basic membrane layer, and part of the polymer membrane structure is easily attacked by free radicals generated in the operation process of the fuel cell; the free radical scavenger in the surface layer of the proton exchange membrane is cerium oxide or manganese oxide nanoparticles, and the free radical capable of degrading the membrane reacts with cerium ions or manganese ions before contacting the membrane through the chemical reaction of the cerium ions or manganese ions and the free radical, so that the damage of the free radical to the membrane is reduced, and the stability of the proton exchange membrane fuel cell is improved; the conductive polymer layer is polyaniline or polypyrrole, the polyaniline or the polypyrrole grows in situ on the surface of the membrane to form a complicated polyaniline layer or a polypyrrole layer, cerium oxide or manganese oxide particles are wrapped, the aggregation of the cerium oxide or manganese oxide particles is prevented, the loss of the free radical scavenger is relieved, the service life of the fuel cell is prolonged, and the stability of the fuel cell is improved.
During the process of scavenging the free radicals, the free radical scavenger can migrate due to the action of water, air flow, electric field and other factors. The surface layer of the conductive polymer layer grown in situ can fix the free radical scavenger in the surface layer, because the conductive polymer layer has a complicated structure and prevents the free radical scavenger from being lost. In addition, the conductive polymer layer is also loose, which does not affect the proton transport process. In the process of in-situ growth of the conductive polymer layer on the surface of the proton exchange membrane, functional groups of the proton exchange membrane can have interaction of electrostatic attraction with groups of the conductive polymer, so that the two are combined very tightly. Meanwhile, due to the coordination effect between the free radical scavenger and the structure of the conductive polymer, the conductive polymer can more effectively fix the free radical scavenger. The experimental results show that: the surface modified proton exchange membrane has excellent free radical scavenging capacity, and the intricate conductive polymer layer can also play a good role in fixing the free radical scavenger, so that the free radical scavenger is prevented from being aggregated, the loss of the free radical scavenger is slowed down, the free radical scavenging capacity of the proton membrane fuel cell is improved, and the chemical stability is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of a PEM with a surface modification layer according to example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a cross section of a proton exchange membrane prepared in example 1 of the present invention;
FIG. 3 is a graph of the conductance of the proton exchange membrane prepared in example 1 of the present invention;
FIG. 4 is the electrochemical performance of the fuel cell with the PEM prepared in example 1 of this invention, (a) is the voltage diagram of the fuel cell with the PEM prepared in example 1 of this invention; (b) is a power density plot of a fuel cell with the proton exchange membrane prepared in example 1 of the present invention;
fig. 5 shows the change of the proton exchange membrane prepared in example 1 of the present invention before and after soaking in the fenton reagent, and (a) shows the change of the mass of the proton exchange membrane prepared in example 1 of the present invention before and after soaking in the fenton reagent; (b) the conductivity of the proton exchange membrane prepared in the embodiment 1 of the invention changes before and after the membrane is soaked in the Fenton reagent;
fig. 6 shows the stability test results of the pem fuel cell prepared in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of an antioxidant proton exchange membrane, which comprises the following steps:
A) adding an oxidant and free radical scavenger nanoparticles into an acid solution to obtain an oxidant solution;
the free radical scavenger nanoparticles are cerium oxide nanoparticles and/or manganese oxide nanoparticles;
B) uniformly mixing an oxidant solution and an acid solution of a conductive polymer monomer to obtain a mixed solution;
C) and respectively adding the mixed solution and an acid solution with the same acid concentration as the mixed solution to the two sides of the proton exchange membrane, and carrying out in-situ growth to form a conductive polymer layer containing the free radical scavenger nanoparticles so as to obtain the antioxidant proton exchange membrane.
The invention firstly prepares an acid solution containing a free radical scavenger and an oxidant, and an acid solution of a conductive polymer monomer.
The acid solution containing the free radical scavenger and the oxidant is prepared according to the following method:
and mixing an oxidant and an acid solution to obtain an acid solution of the oxidant, adding the free radical scavenger nanoparticles, and uniformly stirring at a low temperature to obtain an oxidant mixed solution.
In the invention, the oxidant is preferably ammonium persulfate and/or ferric trichloride; the acid solution is preferably a hydrochloric acid solution or a sulfuric acid solution; the concentration of the acid solution is preferably 0.5-5 mol/L, more preferably 1-4 mol/L, such as 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, and preferably a range value taking any value as an upper limit or a lower limit; in the acid solution of the oxidizing agent, the concentration of the oxidizing agent is preferably 0.05 to 0.5mol/L, more preferably 0.1 to 0.4mol/L, such as 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, and preferably a range value taking any of the above values as an upper limit or a lower limit.
In the present invention, the radical scavenger nanoparticles are preferably cerium oxide nanoparticles and/or manganese oxide nanoparticles.
In the invention, the stirring temperature is preferably 2-8 ℃, more preferably 3-7 ℃, such as 2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃, 7 ℃ and 8 ℃, and is preferably a range value taking any value as an upper limit or a lower limit; the stirring time is preferably 2 to 10 hours, and more preferably 4 to 6 hours.
The acid solution of the conductive polymer monomer is prepared according to the following steps:
and mixing the conducting polymer monomer with an acid solution, and stirring at low temperature in a dark place to obtain the acid solution of the conducting polymer monomer.
In the present invention, the conductive polymer monomer is preferably aniline and/or pyrrole, and the acid solution is preferably a hydrochloric acid solution or a sulfuric acid solution; the concentration of the acid solution is preferably 0.5-5 mol/L, more preferably 1-4 mol/L, such as 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, preferably any of the above values as an upper limit or a lower limit; in the acid solution of the conductive polymer monomer, the concentration of the conductive polymer monomer is preferably 0.05 to 0.5mol/L, more preferably 0.1 to 0.4mol/L, such as 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, and preferably a range value taking any of the above values as an upper limit or a lower limit.
In the invention, the temperature of the low-temperature light-proof stirring is preferably 2-8 ℃, more preferably 3-6 ℃, such as 2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃, 7 ℃ and 8 ℃, and is preferably a range value taking any value as an upper limit or a lower limit; the time for the low-temperature light-proof stirring is preferably 2-10 hours, and more preferably 4-6 hours.
Specifically, in the embodiment of the present invention, the oxidizing agent mixed solution is mixed with the acid solution of the conductive polymer monomer in equal volume, and preferably, the concentrations of the acid solution mixed with the conductive polymer monomer and the acid solution mixed with the oxidizing agent are the same.
More preferably, in the embodiment of the present invention, the oxidant mixed solution and the acid solution of the conducting polymer monomer are added to one side of the proton exchange membrane, respectively, so as to prevent the conducting polymer monomer from polymerizing in the solution under the long-term action of the oxidant, thereby affecting the in-situ growth of the conducting polymer monomer on the surface of the proton exchange membrane.
In the invention, the molar ratio of the conductive polymer monomer to the oxidant is preferably (1-4): 1, more preferably (2-3): 1, such as 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, preferably any of the above values is an upper or lower limit; the molar ratio of the radical scavenger nanoparticles to the conductive polymer monomer is preferably 1: (1-2), more preferably 1: (1.2-1.8) such as 1:1, 1: 1.1,1: 1..2,1: 1.3,1: 1.4,1: 1.5,1: 1.6,1: 1.7,1: 1.8,1: 1.9,1: 2, it is preferably a range value having any of the above numerical values as an upper limit or a lower limit.
And after the mixed solution is obtained, respectively adding the mixed solution and an acid solution with the same concentration as the acid in the mixed solution to both sides of the proton exchange membrane, and performing in-situ growth at a low temperature to form a conductive polymer layer containing the free radical scavenger nanoparticles, thereby obtaining the antioxidant proton exchange membrane.
In the invention, the proton exchange membrane is preferably a perfluorinated sulfonic acid proton exchange membrane or a sulfonated polybiphenyl indole proton exchange membrane, and is prepared by casting a membrane preparation solution obtained by mixing proton exchange membrane polymer powder and an organic solvent.
The functional groups on the surface of the proton exchange membrane can interact with the groups of the conducting polymer by electrostatic attraction, so that the proton exchange membrane grows in situ on the surface of the proton exchange membrane and is very compact.
In the invention, the temperature of the in-situ growth is preferably 2-8 ℃, more preferably 3-7 ℃, such as 2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃, 7 ℃ and 8 ℃, and is preferably a range value taking any value as an upper limit or a lower limit; the time for in-situ growth is preferably 1-10 hours, more preferably 3-8 hours, and more preferably 4-6 hours.
And after in-situ growth is completed, removing the proton exchange membrane, washing with deionized water for 3-5 times, and naturally drying to obtain the antioxidant proton exchange membrane.
The invention also provides an antioxidant proton exchange membrane prepared by the preparation method.
In the invention, the anti-oxidation proton exchange membrane comprises a proton exchange membrane and a conductive polymer layer growing on the surface of the proton exchange membrane in situ;
the conductive polymer layer includes a conductive polymer and a radical scavenger nanoparticle encapsulated within the conductive polymer.
In the present invention, the types and the amounts of the conductive polymer and the radical scavenger nanoparticles are the same as those of the conductive polymer and the radical scavenger nanoparticles described above, and the description of the present invention is omitted here.
The invention also provides a proton exchange membrane fuel cell which comprises the antioxidant proton exchange membrane.
The proton exchange membrane is used as a basic membrane layer, and part of the polymer membrane structure is easily attacked by free radicals generated in the operation process of the fuel cell; the free radical scavenger in the surface layer of the proton exchange membrane is cerium oxide or manganese oxide nanoparticles, and the free radical capable of degrading the membrane reacts with cerium ions or manganese ions before contacting the membrane through the chemical reaction of the cerium ions or manganese ions and the free radical, so that the damage of the free radical to the membrane is reduced, and the stability of the proton exchange membrane fuel cell is improved; the conductive polymer layer is polyaniline or polypyrrole, the polyaniline or the polypyrrole grows in situ on the surface of the membrane to form a complicated polyaniline layer or a polypyrrole layer, cerium oxide or manganese oxide particles are wrapped, the aggregation of the cerium oxide or manganese oxide particles is prevented, the loss of the free radical scavenger is relieved, the service life of the fuel cell is prolonged, and the stability of the fuel cell is improved.
During the process of scavenging the free radicals, the free radical scavenger can migrate due to the action of water, air flow, electric field and other factors. The surface layer of the conductive polymer layer grown in situ can fix the free radical scavenger in the surface layer, because the conductive polymer layer has a complicated structure and prevents the free radical scavenger from being lost. In addition, the conductive polymer layer is also loose, which does not affect the proton transport process. In the process of in-situ growth of the conductive polymer layer on the surface of the proton exchange membrane, the functional groups of the proton exchange membrane and the groups of the conductive polymer have the interaction of electrostatic attraction, so that the two are combined very tightly. Meanwhile, due to the coordination effect between the free radical scavenger and the structure of the conductive polymer, the conductive polymer can more effectively fix the free radical scavenger. The experimental results show that: the surface modified proton exchange membrane has excellent free radical scavenging capacity, and the intricate conductive polymer layer can also play a good role in fixing the free radical scavenger, so that the free radical scavenger is prevented from being aggregated, the loss of the free radical scavenger is slowed down, the free radical scavenging capacity of the proton membrane fuel cell is improved, and the chemical stability is improved.
In order to further illustrate the present invention, the following detailed description is made with reference to the examples to illustrate an oxidation-resistant proton exchange membrane, a preparation method thereof and a proton exchange membrane fuel cell provided by the present invention, but the scope of the present invention should not be construed as being limited thereto.
Example 1
And (2) dissolving the sulfonated polybiphenyl indole (SBPI) proton exchange membrane polymer in a solvent, and carrying out tape casting on a hot plate to obtain the proton exchange membrane.
Dissolving ammonium persulfate solid in 1mol/L hydrochloric acid solution to prepare 0.1mol/L ammonium persulfate hydrochloric acid solution, adding a proper amount of cerium oxide nanoparticles, and stirring at a low temperature of 4 ℃ for 4 hours to uniformly disperse the cerium oxide nanoparticles.
Dissolving aniline in 1mol/L hydrochloric acid solution to prepare 0.1mol/L aniline hydrochloric acid solution, and stirring at low temperature in a dark place for 4h to uniformly disperse aniline.
Adding the obtained solution into one side of a proton exchange membrane according to the ratio of 1:1, standing in a refrigerator at 4 ℃ for 4 hours, taking out the proton exchange membrane with the polyaniline and doped with cerium oxide, washing with deionized water for 3-5 times, and naturally drying.
Proton exchange membrane scanning electron microscope testing
(1) Test method
Taking out the prepared surface modified proton exchange membrane from pure water, placing the membrane in an oven for drying, performing gold spraying treatment, and finally placing the membrane in a scanning electron microscope device for testing to obtain an image of the surface of the proton exchange membrane, as shown in fig. 1, wherein fig. 1 is a scanning electron microscope image of the proton exchange membrane with the surface modified layer in the embodiment 1 of the invention.
Taking out the prepared proton exchange membrane from pure water, placing the proton exchange membrane in an oven for drying, then freezing and breaking the proton exchange membrane by using liquid nitrogen, pasting the obtained section sample on a device with conductive adhesive, spraying gold on the section sample, and finally placing the section sample in a scanning electron microscope device for testing to obtain an image of the section of the proton exchange membrane, wherein the image is shown in figure 2, and figure 2 is a scanning electron microscope image of the section of the proton exchange membrane prepared in the embodiment 1 of the invention.
(2) Results
As shown in fig. 2, the proton exchange membrane layer is disposed on the lower side, and the polyaniline layer coated with cerium oxide nanoparticles is disposed on the upper side. The fact shows that the free radical scavenger existing on the surface of the membrane can play a role in scavenging free radicals in the operation process of the fuel cell, and the intricate polyaniline structure wraps the cerium oxide particles, so that the loss situation of the cerium oxide particles is reduced, and the chemical stability of the proton exchange membrane fuel cell can be improved to a great extent.
Conductivity test
(1) Test method
Cutting the prepared surface modified proton exchange membrane into a size of 1 multiplied by 4cm, soaking the membrane in 1M sulfuric acid solution, changing the sulfuric acid solution once every 1h, soaking the membrane for about 24h, then changing the membrane into deionized water, changing the deionized water once every 1h, soaking the membrane for about 24h, then taking out the membrane, measuring the length and the width of the membrane again, clamping the membrane in a conductivity test instrument, and setting the test current to be 10uA for testing.
(2) Results
As shown in fig. 3, after being soaked in sulfuric acid, the sulfonate proton exchange membrane is converted into hydrogen form, and then the excess acid solution is washed with deionized water, so that the conductivity of the proton exchange membrane with the polyaniline layer growing on the surface is reduced to a certain extent compared with that of the base membrane, because there is interaction between the protonated aniline groups and the sulfonate groups, the aniline groups occupy part of the sulfonate groups, and the conductivity is reduced.
Proton exchange membrane fuel cell performance testing
(1) Test method
Cutting the prepared surface modified proton exchange membrane into a size of 5 multiplied by 5cm, soaking the membrane in 1M sulfuric acid solution, changing the sulfuric acid solution once every 1h, soaking the membrane for about 24h, then changing the deionized water once every 1h, taking out the membrane after soaking the membrane for about 24h, and recording the open-circuit voltage and power density curve of the fuel cell at the temperature of 80 ℃ and 100% RH under the pressure of 0.2 MPa.
(2) Results
As shown in fig. 4, the open-circuit voltage and power density curve of the surface-modified pem fuel cell is improved to some extent compared with that of the unmodified pem.
Accelerated oxidation test
(1) Test method
Drying the prepared surface modified proton exchange membrane, weighing the mass of the proton exchange membrane, testing the conductivity, and immersing the proton exchange membrane into 3% H 2 O 2 ，3ppm Fe 2+ Soaking the membrane in the Fenton reagent at 80 ℃ for 24h, taking out and drying the proton exchange membrane, weighing the mass of the membrane again, testing the conductivity, and carrying out front and back comparison.
(2) Results
As shown in fig. 5a, the mass difference between the surface-modified proton exchange membrane before and after being soaked in the fenton reagent is not large, and as shown in fig. 5b, the conductivity difference between the surface-modified proton exchange membrane before and after being soaked in the fenton reagent is not large, so that the proton exchange membrane doped with the radical scavenger really has a good radical scavenging effect, and can greatly improve the service life of the proton exchange membrane.
Fuel cell stability testing
(1) Test method
Cutting the prepared surface modified proton exchange membrane into a size of 5 multiplied by 5cm, soaking in 1M sulfuric acid solution, changing the sulfuric acid solution once every 1h, changing the sulfuric acid solution into deionized water after soaking for about 24h, changing the deionized water once every 1h, and taking out after soaking for about 24 h. The durability of PEMFCs was tested under the conditions of 80 ℃ and 100% RH. Respectively supplying 0.2 L.min to the anode and the cathode -1 H of (A) 2 And O 2 . At 200mA/cm 2 The voltage of the PEMFC was scanned at a constant current, and the change in voltage thereof was recorded to perform a fuel cell stability test.
(2) Results
As shown in fig. 6, the proton exchange membrane fuel cell after surface modification has no voltage drop when operating for 200 hours under constant current, while the proton exchange membrane without surface modification has severe degradation for about 80 hours, so that the proton exchange membrane after surface modification has significantly improved stability compared with the proton exchange membrane without surface modification.
Example 2
And (2) dissolving the sulfonated polybiphenyl indole (SBPI) proton exchange membrane polymer in a solvent, and performing tape casting on a hot plate to obtain the proton exchange membrane.
Dissolving ammonium persulfate solid in 1M hydrochloric acid solution to prepare 0.1M hydrochloric acid solution of ammonium persulfate, adding a proper amount of manganese oxide nanoparticles, and stirring at low temperature of 4 ℃ for 4 hours to uniformly disperse the manganese oxide nanoparticles.
Dissolving aniline in hydrochloric acid solution with the concentration of 1M to prepare aniline hydrochloric acid solution with the concentration of 0.1M, and stirring at low temperature in a dark place for 4 hours to uniformly disperse aniline.
The solution obtained above was mixed according to the following ratio 1: adding the polyaniline-doped manganese oxide proton exchange membrane into one side of the proton exchange membrane according to the proportion of 1, standing at the temperature of 4 ℃ for 4 hours, taking out the proton exchange membrane on which the polyaniline grows and the manganese oxide is doped, washing with deionized water for 3-5 times, and naturally drying.
Experimental results show that the surface-modified proton exchange membrane prepared by the method has a similar appearance to that of the proton exchange membrane prepared in the embodiment 1, and can remove free radicals in the operation of a fuel cell and improve the stability of the cell.
Example 3
And (2) dissolving the sulfonated polybiphenyl indole (SBPI) proton exchange membrane polymer in a solvent, and performing tape casting on a hot plate to obtain the proton exchange membrane.
Dissolving ammonium persulfate solid in 1M hydrochloric acid solution to prepare 0.1M hydrochloric acid solution of ammonium persulfate, adding a proper amount of cerium oxide nanoparticles, and stirring at a low temperature of 4 ℃ for 4 hours to uniformly disperse the cerium oxide nanoparticles.
Dissolving pyrrole in hydrochloric acid solution with the concentration of 1M to prepare pyrrole hydrochloric acid solution with the concentration of 0.1M, and stirring for 4 hours at low temperature in a dark place to uniformly disperse the pyrrole.
Adding the obtained solution into one side of a proton exchange membrane according to the ratio of 1:1, standing at the temperature of 4 ℃ for 4 hours, taking out the proton exchange membrane with the polypyrrole and doped with cerium oxide, washing with deionized water for 3-5 times, and naturally drying.
Experimental results show that a polypyrrole layer grows on the surface of the proton exchange membrane prepared by the method in situ and is coated with cerium oxide nanoparticles, free radicals can be removed in the operation of a fuel cell, and the stability of the cell is improved.
Example 4
And (2) dissolving the sulfonated polybiphenyl indole (SBPI) proton exchange membrane polymer in a solvent, and performing tape casting on a hot plate to obtain the proton exchange membrane.
Dissolving ammonium persulfate solid in 1M hydrochloric acid solution to prepare 0.1M hydrochloric acid solution of ammonium persulfate, adding a proper amount of manganese oxide nanoparticles, and stirring at low temperature of 4 ℃ for 4 hours to uniformly disperse the manganese oxide nanoparticles.
Dissolving pyrrole in hydrochloric acid solution with the concentration of 1M to prepare pyrrole hydrochloric acid solution with the concentration of 0.1M, and stirring for 4 hours at low temperature in a dark place to uniformly disperse the pyrrole.
Adding the obtained solution into one side of a proton exchange membrane according to the ratio of 1:1, standing at the temperature of 4 ℃ for 8 hours, taking out the proton exchange membrane with the polypyrrole and doped with manganese oxide, washing with deionized water for 3-5 times, and naturally drying.
Experimental results show that a polypyrrole layer grows on the surface of the proton exchange membrane prepared by the method in situ and is coated with manganese oxide nanoparticles, the appearance is similar to that of the polypyrrole layer in example 3, free radicals can be removed in the operation of a fuel cell, and the stability of the cell is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of an oxidation-resistant proton exchange membrane comprises the following steps:
A) adding an oxidant and free radical scavenger nanoparticles into an acid solution to obtain an oxidant mixed solution;
the free radical scavenger nanoparticles are cerium oxide nanoparticles and/or manganese oxide nanoparticles;
B) uniformly mixing the oxidant mixed solution with the acid solution of the conductive polymer monomer to obtain a mixed solution;
C) and respectively adding the mixed solution and an acid solution with the same acid concentration as the mixed solution to the two sides of the proton exchange membrane, and carrying out in-situ growth to form a conductive polymer layer containing the free radical scavenger nanoparticles so as to obtain the antioxidant proton exchange membrane.
2. The production method according to claim 1, wherein the conductive polymer monomer comprises aniline and/or pyrrole;
in the acid solution of the conductive polymer monomer, the concentration of the conductive polymer monomer is 0.05-0.5 mol/L.
3. The method according to claim 2, wherein the acid solution of the conductive polymer monomer is prepared by mixing the conductive polymer monomer with an acid solution;
the acid solution is a hydrochloric acid solution or a sulfuric acid solution, and the concentration of the acid solution is 0.5-5 mol/L.
4. The preparation method according to claim 1, wherein the oxidant is ammonium persulfate and/or ferric trichloride;
the molar ratio of the oxidant to the conductive polymer monomer is 1: (1-4).
5. The method of claim 1, wherein the molar ratio of the radical scavenger nanoparticles to the conductive polymer monomer is 1: (1-2).
6. The preparation method according to claim 1, wherein the in-situ growth temperature is 2-8 ℃; the in-situ growth time is 1-10 hours.
7. The preparation method according to any one of claims 1 to 6, wherein the proton exchange membrane is a perfluorosulfonic acid proton exchange membrane or a sulfonated polybiphenyl indole proton exchange membrane.
8. The oxidation-resistant proton exchange membrane prepared by the preparation method of claim 1, which comprises a proton exchange membrane and a conductive polymer layer growing on the surface of the proton exchange membrane in situ;
the conductive polymer layer includes a conductive polymer and a radical scavenger nanoparticle encapsulated within the conductive polymer.
9. The oxidation-resistant proton exchange membrane according to claim 8 wherein the conductive polymer layer has a thickness of 400 to 500 nm.
10. A proton exchange membrane fuel cell comprising the oxidation resistant proton exchange membrane of claim 8 or 9.
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