CN115084608B - Antioxidant proton exchange membrane, preparation method thereof and proton exchange membrane fuel cell - Google Patents
Antioxidant proton exchange membrane, preparation method thereof and proton exchange membrane fuel cell Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 175
- 239000000446 fuel Substances 0.000 title claims abstract description 45
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 89
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 77
- 239000002516 radical scavenger Substances 0.000 claims abstract description 56
- 239000002105 nanoparticle Substances 0.000 claims abstract description 51
- 229940123457 Free radical scavenger Drugs 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 46
- 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
- 239000007800 oxidant agent Substances 0.000 claims abstract description 32
- 238000011065 in-situ storage Methods 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 23
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 22
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 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 19
- 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
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- XLUAOPYZCRBSPN-UHFFFAOYSA-N 1,1'-biphenyl;1h-indole Chemical group C1=CC=C2NC=CC2=C1.C1=CC=CC=C1C1=CC=CC=C1 XLUAOPYZCRBSPN-UHFFFAOYSA-N 0.000 claims description 7
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 8
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 35
- 150000003254 radicals Chemical class 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- -1 hydroxyl radicals Chemical class 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229920000767 polyaniline Polymers 0.000 description 11
- 238000002791 soaking Methods 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 229920000128 polypyrrole Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000002000 scavenging effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000012028 Fenton's reagent Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 238000010345 tape casting Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 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
- 230000000694 effects Effects 0.000 description 3
- 238000013112 stability test Methods 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
- 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
- 230000000593 degrading effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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
- H01M8/1069—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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
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 nano-particles are cerium oxide nano-particles and/or manganese oxide nano-particles; b) Uniformly mixing an oxidant solution and an acid solution of a conductive polymer monomer to obtain a mixed solution; c) Adding a mixed solution to one side of the proton exchange membrane, and performing in-situ growth to form a conductive polymer layer containing free radical scavenger nano particles, thereby obtaining the antioxidant proton exchange membrane. The proton exchange membrane is used as a basic membrane layer, the conductive polymer grows in situ on the surface of the membrane, so that the particles of the free radical scavenger are wrapped, the aggregation of the 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. The invention also provides an oxidation-resistant 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
A Proton Exchange Membrane Fuel Cell (PEMFC) is a device for converting chemical energy into electric energy by taking hydrogen as fuel, wherein a proton exchange membrane is a core unit of the proton exchange membrane fuel cell, and is used for conducting protons to form a cell loop, and meanwhile, the anode and cathode of the fuel cell can be separated, so that the conductivity and the stability of the proton exchange membrane have very important significance.
During operation of the fuel cell, incomplete reaction of the cathode side oxygen with protons generates hydrogen peroxide, further reaction of the hydrogen peroxide generates hydroxyl radicals and hydrogen peroxide radicals, and hydrogen radicals are formed on the surface of the catalyst layer at the anode side, the hydrogen radicals react with oxygen permeated from the cathode side to generate hydrogen peroxide radicals, wherein part of the hydrogen peroxide radicals react with hydrogen ions to generate hydrogen peroxide, and further the same reaction as the anode side generates hydroxyl radicals and hydrogen peroxide radicals.
The conventional proton exchange membrane is easy to attack by free radicals due to the structures such as ether bonds, carbon-sulfur bonds, benzene rings and the like in the structure, so that the polymer chains are degraded, the stability of the proton exchange membrane is reduced, and the performance of the fuel cell is unstable.
Disclosure of Invention
The invention aims to provide an oxidation-resistant proton exchange membrane, a preparation method thereof and a proton exchange membrane fuel cell, and the oxidation-resistant proton exchange membrane can solve the technical problems that the proton exchange membrane fuel cell is attacked by free radicals in the operation process and the chemical stability is reduced.
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 nano particles into an acid solution to obtain an oxidant mixed solution;
the free radical scavenger nano-particles are cerium oxide nano-particles and/or manganese oxide nano-particles;
B) Uniformly mixing the oxidant mixed solution with an acid solution of the conductive polymer monomer to obtain a mixed solution;
c) And respectively adding a mixed solution and an acid solution with the same acid concentration as the mixed solution into two sides of the proton exchange membrane, and performing in-situ growth to form a conductive polymer layer containing free radical scavenger nano particles, thereby obtaining the antioxidant proton exchange membrane.
Preferably, 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.
Preferably, the acid solution of the conductive polymer monomer is prepared by mixing the conductive polymer monomer with the acid solution;
The acid solution is hydrochloric acid solution or 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 poly biphenyl 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 grown on the surface of the proton exchange membrane in situ;
The conductive polymer layer includes a conductive polymer and free radical scavenger nanoparticles encapsulated within the conductive polymer.
Preferably, the thickness of the conductive polymer layer is 400 to 500nm.
The present invention provides a proton exchange membrane fuel cell comprising an oxidation resistant proton exchange membrane as described above.
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 nano-particles are cerium oxide nano-particles and/or manganese oxide nano-particles; b) Uniformly mixing an oxidant solution and an acid solution of a conductive polymer monomer to obtain a mixed solution; c) Adding a mixed solution to one side of the proton exchange membrane, and performing in-situ growth to form a conductive polymer layer containing free radical scavenger nano particles, thereby obtaining the antioxidant proton exchange membrane. The proton exchange membrane is adopted as a basic membrane layer, and part of structures in the polymer membrane structure are easy to attack 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 nano particles, and cerium ions or manganese ions and free radicals are subjected to chemical reaction, so that the free radicals capable of degrading the membrane react with cerium ions or manganese ions before contacting the membrane, the damage 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 polypyrrole grows in situ on the surface of the membrane to form a complicated polyaniline layer or polypyrrole layer, cerium oxide or manganese oxide particles are wrapped, the cerium oxide or manganese oxide particles are prevented from being aggregated, meanwhile, the loss of the free radical scavenger is relieved, the service life of the fuel cell is prolonged, the stability of the fuel cell is improved, and in-situ growing of the conductive polymer and doping of the free radical scavenger proton membrane fuel cell have excellent chemical stability.
In the process of scavenging free radicals by the free radical scavenger, the free radical scavenger can migrate due to the effects of factors such as water, air flow, electric field and the like. The conductive polymer layer with the in-situ grown surface layer can fix the free radical scavenger therein, because the conductive polymer layer has a complicated structure, and the loss of the free radical scavenger is prevented. 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 can have electrostatic attraction interaction with the groups of the conductive polymer, so that the two are tightly combined. Meanwhile, due to coordination between the free radical scavenger and the conductive polymer structure, the conductive polymer can fix the free radical scavenger more effectively. The experimental results show that: the surface modified proton exchange membrane has excellent capability of scavenging free radicals, and meanwhile, the complicated conductive polymer layer can also play a role of well fixing the free radical scavenger, so that the free radical scavenger is prevented from gathering and is slowed down, the loss of the free radical scavenger is slowed down, the capability of scavenging free radicals 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 that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of a proton exchange membrane 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 showing the conductance of the proton exchange membrane prepared in example 1 of the present invention;
FIG. 4 shows the electrochemical performance of the fuel cell of the proton exchange membrane prepared in example 1 of the present invention, (a) shows the voltage diagram of the fuel cell of the proton exchange membrane prepared in example 1 of the present invention; (b) A power density map of a fuel cell for a 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 the Fenton reagent, (a) shows the change of the mass of the proton exchange membrane prepared in example 1 of the present invention before and after soaking the Fenton reagent; (b) Conductivity changes before and after soaking Fenton reagent for the proton exchange membrane prepared in the embodiment 1 of the invention;
fig. 6 shows the stability test results of the proton exchange membrane 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 nano-particles are cerium oxide nano-particles and/or manganese oxide nano-particles;
B) Uniformly mixing an oxidant solution and an acid solution of a conductive polymer monomer to obtain a mixed solution;
c) And respectively adding a mixed solution and an acid solution with the same acid concentration as the mixed solution into two sides of the proton exchange membrane, and performing in-situ growth to form a conductive polymer layer containing free radical scavenger nano particles, thereby obtaining 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 by the following method:
mixing an oxidant with the acid solution to obtain an acid solution of the oxidant, adding the free radical scavenger nano particles, and uniformly stirring at a low temperature to obtain an oxidant mixed solution.
In the present invention, the oxidizing agent is preferably ammonium persulfate and/or ferric trichloride; the acid solution is preferably hydrochloric acid solution or sulfuric acid solution; the concentration of the acid solution is preferably 0.5 to 5mol/L, more preferably 1 to 4mol/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 a range value having any of the above values as an upper limit or a lower limit; the concentration of the oxidizing agent in the acid solution 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, preferably a range value in which any of the above values is 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 present invention, the temperature of the stirring is preferably 2 to 8 ℃, more preferably 3 to 7 ℃, such as 2 ℃,3 ℃,4 ℃,5 ℃,6 ℃,7 ℃,8 ℃, preferably a range value in which any of the above values is an upper limit or a lower limit; the stirring time is preferably 2 to 10 hours, more preferably 4 to 6 hours.
The acid solution of the conductive polymer monomer is prepared by the following steps:
And mixing the conductive polymer monomer with an acid solution, and stirring at a low temperature in a dark place to obtain the acid solution of the conductive polymer monomer.
In the present invention, the conductive polymer monomer is preferably aniline and/or pyrrole, and the acid solution is preferably hydrochloric acid solution or sulfuric acid solution; the concentration of the acid solution is preferably 0.5 to 5mol/L, more preferably 1 to 4mol/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 a range value having 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, preferably a range value in which any of the above values is an upper limit or a lower limit.
In the present invention, the temperature of the low-temperature light-shielding stirring is preferably 2 to 8 ℃, more preferably 3 to 6 ℃, such as 2 ℃,3 ℃,4 ℃,5 ℃,6 ℃,7 ℃,8 ℃, preferably a range value with any of the above values as an upper limit or a lower limit; the time for stirring at a low temperature in the dark is preferably 2 to 10 hours, more preferably 4 to 6 hours.
Specifically, in the embodiment of the present invention, the mixed solution of the oxidizing agent and the acid solution of the conductive polymer monomer are mixed in equal volumes, and preferably, the concentration of the acid solution mixed with the conductive polymer monomer and the concentration of the acid solution mixed with the oxidizing agent are the same.
More preferably, in the embodiment of the present invention, an acid solution of the mixed solution of the oxidizing agent and the conductive polymer monomer is added to one side of the proton exchange membrane, so as to avoid polymerization of the conductive polymer monomer in the solution under the long-term action of the oxidizing agent, thereby affecting in-situ growth of the conductive polymer monomer on the surface of the proton exchange membrane.
In the present invention, the molar ratio of the conductive polymer monomer to the oxidizing agent is preferably (1 to 4): 1, more preferably (2 to 3): 1, such as 1:1,1.5:1,2:1,2.5:1,3:1,3.5:1,4:1, preferably ranges having any of the above values as 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, preferably a range value having any of the above values as an upper limit or a lower limit.
After the mixed solution is obtained, the mixed solution and an acid solution with the same concentration as that in the mixed solution are respectively added to the two sides of the proton exchange membrane, and in-situ growth is carried out at low temperature to form a conductive polymer layer containing the free radical scavenger nano particles, thus obtaining the antioxidant proton exchange membrane.
In the invention, the proton exchange membrane is preferably a perfluorosulfonic acid proton exchange membrane or a sulfonated poly biphenyl indole proton exchange membrane, and is prepared by casting membrane preparation liquid obtained by mixing proton exchange membrane polymer powder with an organic solvent.
The functional groups on the surface of the proton exchange membrane can have electrostatic attraction interaction with the groups of the conductive polymer, so that the functional groups grow on the surface of the proton exchange membrane in situ and are very compact.
In the present invention, the in-situ growth temperature is preferably 2 to 8 ℃, more preferably 3 to 7 ℃, such as 2 ℃,3 ℃,4 ℃,5 ℃,6 ℃,7 ℃,8 ℃, preferably a range value with any of the above values as an upper limit or a lower limit; the time for the in-situ growth is preferably 1 to 10 hours, more preferably 3 to 8 hours, and still more preferably 4 to 6 hours.
After the in-situ growth is completed, the proton exchange membrane is removed, the proton exchange membrane is washed for 3 to 5 times by deionized water, and the antioxidation proton exchange membrane can be obtained by natural air drying.
The invention also provides an oxidation-resistant proton exchange membrane which is prepared according to the preparation method.
In the invention, the oxidation-resistant proton exchange membrane comprises a proton exchange membrane and a conductive polymer layer grown on the surface of the proton exchange membrane in situ;
The conductive polymer layer includes a conductive polymer and free radical scavenger nanoparticles encapsulated within the conductive polymer.
In the present invention, the types and 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 present invention is not repeated herein.
The invention also provides a proton exchange membrane fuel cell comprising the antioxidant proton exchange membrane.
The proton exchange membrane is adopted as a basic membrane layer, and part of structures in the polymer membrane structure are easy to attack 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 nano particles, and cerium ions or manganese ions and free radicals are subjected to chemical reaction, so that the free radicals capable of degrading the membrane react with cerium ions or manganese ions before contacting the membrane, the damage 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 polypyrrole grows in situ on the surface of the membrane to form a complicated polyaniline layer or polypyrrole layer, cerium oxide or manganese oxide particles are wrapped, the cerium oxide or manganese oxide particles are prevented from being aggregated, meanwhile, the loss of the free radical scavenger is relieved, the service life of the fuel cell is prolonged, the stability of the fuel cell is improved, and in-situ growing of the conductive polymer and doping of the free radical scavenger proton membrane fuel cell have excellent chemical stability.
In the process of scavenging free radicals by the free radical scavenger, the free radical scavenger can migrate due to the effects of factors such as water, air flow, electric field and the like. The conductive polymer layer with the in-situ grown surface layer can fix the free radical scavenger therein, because the conductive polymer layer has a complicated structure, and the loss of the free radical scavenger is prevented. 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 can have electrostatic attraction interaction with the groups of the conductive polymer, so that the two are tightly combined. Meanwhile, due to coordination between the free radical scavenger and the conductive polymer structure, the conductive polymer can fix the free radical scavenger more effectively. The experimental results show that: the surface modified proton exchange membrane has excellent capability of scavenging free radicals, and meanwhile, the complicated conductive polymer layer can also play a role of well fixing the free radical scavenger, so that the free radical scavenger is prevented from gathering and is slowed down, the loss of the free radical scavenger is slowed down, the capability of scavenging free radicals of the proton membrane fuel cell is improved, and the chemical stability is improved.
In order to further illustrate the present invention, the following examples are provided to describe an oxidation-resistant proton exchange membrane, its preparation method and proton exchange membrane fuel cell in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
And dissolving the sulfonated poly biphenyl 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 nano particles, and stirring at a low temperature of 4 ℃ for 4 hours to uniformly disperse the cerium oxide nano particles.
Dissolving aniline in 1mol/L hydrochloric acid solution to prepare 0.1mol/L aniline hydrochloric acid solution, and stirring for 4 hours at a low temperature Wen Biguang to uniformly disperse the 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 which grows with polyaniline and is doped with cerium oxide, washing with deionized water for 3-5 times, and naturally air-drying.
Proton exchange membrane scanning electron microscope test
(1) Test method
Taking out the prepared surface modified proton exchange membrane from pure water, drying in an oven, performing metal spraying treatment on the proton exchange membrane, and finally placing the proton exchange membrane in a device of a scanning electron microscope for testing to obtain an image of the surface of the proton exchange membrane, wherein fig. 1 is a scanning electron microscope image of the proton exchange membrane with a surface modification layer in embodiment 1 of the invention.
Taking out the prepared proton exchange membrane from pure water, putting the proton exchange membrane into an oven for drying, freezing and breaking the proton exchange membrane by liquid nitrogen, pasting the obtained section sample on a device with conductive adhesive, performing metal spraying treatment on the section sample, and finally putting the section sample into a device of a scanning electron microscope for testing to obtain an image of the section of the proton exchange membrane, wherein the image is shown in fig. 2, and fig. 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 lower side is a proton exchange membrane layer, and the upper side is a polyaniline layer coated with cerium oxide nanoparticles. The method shows that the existence of the free radical scavenger on the surface of the membrane can play a role in scavenging free radicals in the operation process of the fuel cell, and the cerium oxide particles are wrapped in the membrane by the complicated polyaniline structure, so that the loss condition of the cerium oxide particles is reduced, and the chemical stability of the proton exchange membrane fuel cell can be greatly improved.
Conductivity test
(1) Test method
The prepared surface modified proton exchange membrane is cut out to be 1 multiplied by 4cm, soaked in 1M sulfuric acid solution, the sulfuric acid solution is changed every 1h, deionized water is changed after soaking for about 24h, the deionized water is changed every 1h, the surface modified proton exchange membrane is taken out after soaking for about 24h, the length and the width of the surface modified proton exchange membrane are measured again, the surface modified proton exchange membrane is clamped into a conductivity test instrument, and the test current is set to be 10uA for testing.
(2) Results
As shown in fig. 3, after the proton exchange membrane of the sulfonate type is converted into the hydrogen type after being soaked in sulfuric acid, and then the redundant acid solution is washed by deionized water, the conductivity of the proton exchange membrane with the polyaniline layer grown on the surface can be seen to be reduced to a certain extent compared with that of the base membrane, because of the interaction between the protonated anilino group and the sulfonate group, the anilino group occupies part of the sulfonate group, and the conductivity is reduced.
Proton exchange membrane fuel cell performance test
(1) Test method
The prepared surface modified proton exchange membrane is cut out to be 5 multiplied by 5cm, soaked in 1M sulfuric acid solution, the sulfuric acid solution is changed every 1h, deionized water is changed every 1h after soaking for about 24h, the deionized water is changed every 1h, the membrane is taken out after soaking for about 24h, and the open circuit voltage and power density curve of the fuel cell are recorded at 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 curves of the surface modified proton exchange membrane fuel cell are improved to some extent compared with those of the unmodified proton exchange membrane.
Accelerated oxidation test
(1) Test method
And (3) drying the prepared surface modified proton exchange membrane, weighing the mass of the proton exchange membrane, testing the conductivity, immersing the proton exchange membrane in a Fenton reagent of 3%H 2O2,3ppm Fe2+, immersing the proton exchange membrane for 24 hours at 80 ℃, taking out the proton exchange membrane, drying the proton exchange membrane, weighing the mass of the proton exchange membrane again, testing the conductivity, and comparing the proton exchange membrane before and after.
(2) Results
As shown in fig. 5a, the quality of the proton exchange membrane after surface modification is not much different before and after soaking in the Fenton reagent, and as shown in fig. 5b, the conductivity of the proton exchange membrane after surface modification is not much different before and after soaking in the Fenton reagent, therefore, the proton exchange membrane doped with the free radical scavenger has good effect of scavenging free radicals, and can greatly improve the service life of the proton exchange membrane.
Fuel cell stability test
(1) Test method
The prepared surface modified proton exchange membrane is cut out to be 5 multiplied by 5cm, soaked in 1M sulfuric acid solution, the sulfuric acid solution is changed every 1h, deionized water is changed after soaking for about 24h, the deionized water is changed every 1h, and the membrane is taken out after soaking for about 24 h. The durability of PEMFCs was tested at 80 ℃ and 100% rh. H 2 and O 2 of 0.2L min -1 were supplied to the anode and cathode, respectively. The voltage of the PEMFC was scanned at a constant current of 200mA/cm 2 and the change in the voltage thereof was recorded to conduct 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 during operation for 200 hours under constant current, while the unmodified proton exchange membrane has serious degradation at about 80 hours, so that the surface modified proton exchange membrane has obvious stability improvement compared with the unmodified proton exchange membrane.
Example 2
And dissolving the sulfonated poly biphenyl 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 1M hydrochloric acid solution to prepare 0.1M ammonium persulfate hydrochloric acid solution, adding a proper amount of manganese oxide nano particles, and stirring at a low temperature of 4 ℃ for 4 hours to uniformly disperse the manganese oxide nano particles.
Dissolving aniline in 1M hydrochloric acid solution to prepare 0.1M aniline hydrochloric acid solution, and stirring for 4 hours with low Wen Biguang to uniformly disperse the aniline.
The solution obtained above was prepared according to 1:1, standing at the temperature of 4 ℃ for 4 hours, taking out the proton exchange membrane which grows with polyaniline and is doped with manganese oxide, washing 3-5 times with deionized water, and naturally air-drying.
Experimental results show that the surface modified proton exchange membrane prepared by the method has similar morphology as in the embodiment 1, and can remove free radicals in the operation of the fuel cell, so that the stability of the cell is improved.
Example 3
And dissolving the sulfonated poly biphenyl 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 1M hydrochloric acid solution to prepare 0.1M ammonium persulfate hydrochloric acid solution, adding a proper amount of cerium oxide nano particles, and stirring at a low temperature of 4 ℃ for 4 hours to uniformly disperse the cerium oxide nano particles.
Pyrrole is dissolved in 1M hydrochloric acid solution to prepare 0.1M pyrrole hydrochloric acid solution, and the solution is stirred for 4 hours with low Wen Biguang to ensure that the solution is uniformly dispersed.
Adding the obtained solution into one side of a proton exchange membrane according to the proportion of 1:1, standing at the temperature of 4 ℃ for 4 hours, taking out the proton exchange membrane which grows with polypyrrole and is doped with cerium oxide, washing with deionized water for 3-5 times, and naturally air-drying.
Experimental results show that the proton exchange membrane prepared by the method has a polypyrrole layer grown on the surface in situ and is coated with cerium oxide nano particles, so that free radicals can be removed in the operation of a fuel cell, and the stability of the cell is improved.
Example 4
And dissolving the sulfonated poly biphenyl 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 1M hydrochloric acid solution to prepare 0.1M ammonium persulfate hydrochloric acid solution, adding a proper amount of manganese oxide nano particles, and stirring at a low temperature of 4 ℃ for 4 hours to uniformly disperse the manganese oxide nano particles.
Pyrrole is dissolved in 1M hydrochloric acid solution to prepare 0.1M pyrrole hydrochloric acid solution, and the solution is stirred for 4 hours with low Wen Biguang to ensure that the solution is uniformly dispersed.
Adding the obtained solution into one side of a proton exchange membrane according to the proportion of 1:1, standing at the temperature of 4 ℃ for 8 hours, taking out the proton exchange membrane which grows with polypyrrole and is doped with manganese oxide, washing with deionized water for 3-5 times, and naturally air-drying.
Experimental results show that the proton exchange membrane prepared by the method has a polypyrrole layer grown on the surface in situ and coated with manganese oxide nano particles, has a morphology similar to that of the embodiment 3, and can remove free radicals in the operation of the fuel cell, so that the stability of the cell is improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The preparation method of the antioxidant proton exchange membrane comprises the following steps:
a) Adding an oxidant and free radical scavenger nano particles into an acid solution to obtain an oxidant mixed solution;
the free radical scavenger nano-particles are cerium oxide nano-particles and/or manganese oxide nano-particles;
B) Uniformly mixing the oxidant mixed solution with an acid solution of the conductive polymer monomer to obtain a mixed solution;
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;
The acid solution of the conductive polymer monomer is prepared by mixing the conductive polymer monomer with the acid solution; the acid solution is hydrochloric acid solution or sulfuric acid solution, and the concentration of the acid solution is 0.5-5 mol/L;
c) And respectively adding a mixed solution and an acid solution with the same acid concentration as the mixed solution into two sides of the proton exchange membrane, and performing in-situ growth to form a conductive polymer layer containing free radical scavenger nano particles, thereby obtaining the antioxidant proton exchange membrane.
2. The method according to claim 1, wherein the oxidizing agent is ammonium persulfate and/or ferric trichloride;
The molar ratio of the oxidant to the conductive polymer monomer is 1: (1-4).
3. The method of claim 1, wherein the molar ratio of the radical scavenger nanoparticles to the conductive polymer monomer is 1: (1-2).
4. The method of claim 1, wherein the in-situ growth temperature is 2-8 ℃; the in-situ growth time is 1-10 hours.
5. The method according to any one of claims 1 to 4, wherein the proton exchange membrane is a perfluorosulfonic acid proton exchange membrane or a sulfonated poly biphenyl indole proton exchange membrane.
6. The oxidation-resistant proton exchange membrane prepared by the preparation method of claim 1, comprising a proton exchange membrane and a conductive polymer layer grown on the surface of the proton exchange membrane in situ;
The conductive polymer layer includes a conductive polymer and free radical scavenger nanoparticles encapsulated within the conductive polymer.
7. An oxidation resistant proton exchange membrane according to claim 6, wherein the thickness of the conductive polymer layer is 400-500 nm.
8. A proton exchange membrane fuel cell comprising the oxidation resistant proton exchange membrane of claim 6 or 7.
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