CN113690450A - Free radical quenching agent, preparation method thereof and application thereof in membrane electrode - Google Patents
Free radical quenching agent, preparation method thereof and application thereof in membrane electrode Download PDFInfo
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- 150000003254 radicals Chemical class 0.000 title claims abstract description 95
- 239000012528 membrane Substances 0.000 title claims abstract description 63
- 238000010791 quenching Methods 0.000 title claims abstract description 49
- 230000000171 quenching effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000013543 active substance Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 20
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 7
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000000903 blocking effect Effects 0.000 claims abstract description 4
- 239000006229 carbon black Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 17
- 238000005507 spraying Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- -1 phosphate compound Chemical class 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 3
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 150000003460 sulfonic acids Chemical class 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001785 cerium compounds Chemical group 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003658 tungsten compounds Chemical class 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
-
- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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 discloses a free radical quencher which comprises a carrier and an active substance, wherein the carrier is carbon black, carbon nano tube or graphene, and the active substance is CeO2、MnO2、WO3、Fe3O4、RuO2The content of the active substance is 10-60 wt%. The invention also discloses a preparation method of the free radical quenching agent. The invention also discloses the application of the free radical quenching agent in a membrane electrode, namely the free radical quenching agent is sprayed on two sides of a proton exchange membrane and used for blocking free radical attack and corroding groups on perfluorosulfonic acid of the proton exchange membrane. The invention solves the migration problem of the free radical quenching agent and the problem of low activity of the free radical quenching agent, and constructs a novel membrane electrodeThe structure protects the perfluorinated sulfonic acid resin group on the proton membrane, and the perfluorinated sulfonic acid resin group is attacked and corroded by free radicals as little as possible, so that the performance of the membrane electrode is finally improved, and the defect of life attenuation is overcome.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a free radical quencher, a preparation method thereof and application thereof in a membrane electrode.
Background
Commonly used free radical quenchers include CeO2、MnO2、WO3、Fe3O4、RuO2And the like, mainly in the form of particles, and are generally added to a catalyst layer or a proton exchange membrane. There are generally three major problems with the use of free radical quenchers: firstly, when the MEA works, the granular radical quenching agent can migrate due to the existence of internal water and gas; secondly, the activity of the free radical quencher is low due to poor conductivity of the free radical quencher in an oxide state; and thirdly, the addition amount of the free radical quenching agent in the catalyst layer is too high, so that the electrochemical reaction activity is reduced, and the output voltage of the membrane electrode is low. The three reasons affect the wide application of the free radical quenching agent, and the hydroxyl free radicals generated in the catalyst layer corrode the proton membrane, so that the performance and the service life of the current membrane electrode are seriously reduced.
The existing free radical quenching agent is not applied in a large scale, most of the free radical quenching agents are added into a proton exchange membrane in a particle mode, but the particle free radical quenching agents can migrate due to the existence of moisture when the proton membrane works, so that the performance and the service life of the proton membrane are influenced. Chinese patent ZL200780031657.2 discloses a reinforced electrolyte membrane for fuel cell, which is fixed in the PTFE reinforced layer of the proton exchange membrane by a particulate radical quencher, which alleviates the migration of the quencher, but affects the performance of the quencher because hydroxyl radicals are generated in the catalyst layer and the radicals corrode the terminal carboxyl groups, sulfonate groups, ether bonds of the side chains and tertiary carbon bonds of the main chain on the perfluorosulfonic acid of the proton membrane. The free radical quencher in the PTFE enhanced layer has a certain distance from the perfluorosulfonic acid, so the free radical quencher is difficult to quench free radicals in time, and in addition, the proton membrane is an electronic insulator, so electrons are difficult to conduct, and the performance of the free radical quencher can be influenced.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a free radical quencher and a preparation method thereof.
The invention also aims to provide the application of the free radical quenching agent in membrane electrode.
The design idea of the invention is as follows: first, a suitable, non-migrating support is selected, carbon nanotubes and graphene being preferred. And then carrying out oxidation treatment on the carrier. Then loading the active substance on the carrier by a liquid phase synthesis method. And spraying the free radical quenching agent on two sides of the proton exchange membrane by a spraying method, finally preparing the membrane electrode, and testing the output voltage and the durability of the membrane electrode.
The technical scheme of the invention is as follows:
the free radical quencher comprises a carrier and an active substance, wherein the carrier is carbon black, carbon nano tubes or graphene, and the active substance is CeO2、MnO2、WO3、Fe3O4、RuO2The free radical quenching agent comprises one or more of a noble metal phosphate compound, a metal phosphate compound or a metal fluoride, and the content of active substances in the free radical quenching agent is 10-60 wt%.
Furthermore, the active substance of the free radical quencher is nano-particles, and the particle size of the active substance is 1-50 nm.
Further, the carrier is carbon nano tube or graphene; the active material being CeO2Or MnO2(ii) a The content of active substances in the free radical quencher is 10-30 wt%.
A method of preparing a free radical quencher, the method comprising:
carrying out oxidation treatment on the carrier;
by the liquid phase synthesis method, an alkaline agent deposits an active substance precursor on the carrier, and the active substance precursor is reduced or oxidized again to load an active substance on the carrier.
Further, the carrier is treated in 1-5mol/L oxidant, and the treatment temperature is 50-130 ℃;
and drying the treated carrier, mixing the dried carrier with an active substance precursor, adding a hydroalcoholic solution and an alkaline reagent, and reacting for 2-10h at the temperature of 120-180 ℃ to generate the free radical quencher.
Further, the oxidant is any one of nitric acid, sulfuric acid, perchloric acid, hydrogen peroxide, potassium dichromate or potassium permanganate;
the mass ratio of the active substance/(active substance + carrier) is 10-60 wt%; the alkaline reagent is any one of sodium hydroxide, potassium hydroxide or ammonia water; the volume ratio of the water, the alcohol and the alkaline reagent is (40-60): (20-30): (1-5).
Further, the oxidant is any one of nitric acid, sulfuric acid or hydrogen peroxide.
The application of the free radical quencher in the membrane electrode is characterized in that a reaction layer of the free radical quencher is arranged on the surface of a proton exchange membrane of the membrane electrode and is used for blocking free radicals from attacking and corroding groups on perfluorosulfonic acid of the proton exchange membrane.
Further, the radical quencher is sprayed on both sides of the proton exchange membrane: preparing slurry by a free radical quenching agent, and then spraying by adopting a spraying process.
Further, the spraying thickness of the free radical quenching agent is 200nm-2 μm.
The invention has the following beneficial effects:
the invention solves the migration problem of the free radical quenching agent and the problem of low activity of the free radical quenching agent, constructs the structure of a novel membrane electrode, protects the perfluorinated sulfonic acid resin group on the proton membrane, suffers the attack and corrosion of free radicals as little as possible, finally improves the performance of the membrane electrode and overcomes the defect of life attenuation.
The free radical quencher of the invention improves the performance by changing the structure, prepares nanometer oxide particles, selects a proper carrier, and can avoid the migration because the carrier needs to meet the requirements of high conductivity and stable structure.
The membrane electrode optimally designs the structure, and by blocking and quenching hydroxyl radicals (a free radical quenching layer is constructed on the surface of the proton membrane, the free radicals are blocked from attacking and corroding groups on perfluorosulfonic acid of the proton membrane).
Drawings
Fig. 1 is a graph showing membrane electrode durability data of each example and comparative example.
FIG. 2 is a schematic diagram of the membrane electrode structure, wherein the first is a proton exchange membrane, the second is a radical quenching layer, the third is a catalyst layer, and the fourth is a gas diffusion layer.
FIG. 3 is a schematic structural diagram of a free radical quencher, wherein [. sup. ] is a carrier, and [. sup. ] is an active substance particle.
Fig. 4 is a tem image of the radical quencher of example 1, wherein is graphene and is manganese dioxide particles.
FIG. 5 is a TEM image of the radical quencher in example 2, wherein nino is carbon nanotubes and particles of cerium oxide are produced.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples.
The free radical quencher comprises a carrier and an active substance, wherein the particle size of the active substance of the free radical quencher is 1-50nm, the active substance is loaded on the carrier, oxygen-containing functional groups and defects exist on the carrier, and the active substance can be anchored and combined with the carrier.
Wherein the kind of the carrier is as follows: carbon black, carbon nanotubes, graphene, and the like, and a preferable carrier is carbon nanotubes or graphene.
Kind of active substance: CeO (CeO)2、MnO2、WO3、Fe3O4、RuO2One or more of noble metal phosphate compound, metal phosphate compound or metal fluoride, preferably, the active material is CeO2Or MnO2。
The content of the oxide (i.e. active substance) in the free radical quencher is 10-60 wt%, preferably 10-30 wt%.
The invention also provides a preparation method of the free radical quenching agent, which adopts a liquid phase method and comprises the following steps:
(1) and (3) carrier treatment: commercial carriers are treated for 1 to 5 hours in 1 to 5mol/L oxidant at 50 to 130 ℃, and then dried overnight at 60 to 90 ℃ to remove water.
This step requires treatment of the commercial support because the commercial support has limited surface defects and fewer oxygen-containing groups, while surface treatment of the commercial support with an oxidizing agent increases surface defects and oxygen-containing groups.
The oxidant is any one of nitric acid, sulfuric acid, perchloric acid, hydrogen peroxide, potassium dichromate or potassium permanganate. Preferably, the oxidant is nitric acid, sulfuric acid or hydrogen peroxide.
(2) Synthesizing a free radical quencher: mixing the treated carrier and the active substance precursor, wherein the mass ratio of active substance/(active substance + carrier) is 10-60 wt%, adding a hydroalcoholic solution and an alkaline reagent, and reacting at the temperature of 120-.
The step adopts a liquid phase method, an alkaline reagent settles metal ions (contained in an active substance precursor), the metal ions settle on a carbon carrier, and the metal ions are reduced and oxidized under the action of alcohol and high temperature and high pressure.
Wherein the active material precursor is a cerium compound, a manganese compound, a tungsten compound, an iron compound, a ruthenium compound, or the like: cerium is exemplified by cerium nitrate, cerium chloride, cerium sulfate, and the like.
The alkaline reagent is sodium hydroxide, potassium hydroxide or ammonia water, etc.
The hydroalcoholic solution is a mixture of water and alcohol, and the volume ratio of water, alcohol and alkaline reagent is (40-60): (20-30): (1-5).
The invention also provides the application of the free radical quenching agent in a membrane electrode, wherein a free radical quenching agent layer is constructed on the surface of a proton exchange membrane, namely the free radical quenching agent is sprayed on two sides of the proton exchange membrane, the thickness is 200nm-2 mu m, and the free radical is blocked from attacking and corroding groups on perfluorosulfonic acid of the proton exchange membrane.
Example 1:
10g of graphene is firstly treated in 3mol/L sulfuric acid at 120 ℃ for 2h, and then is washed, filtered and dried at 75 ℃ overnight. Weighing 5g of the acid-treated graphene and 7.65g of manganese dichloride in 1L of hydroalcoholic solution, adding 50ml of ammonia water, and treating at 150 ℃ for 3h in a reaction kettle to prepare 40 wt% of MnO 2/graphene, namely the free radical quencher.
Fig. 4 is a transmission electron microscope picture of the present example, in which manganese dioxide particles 8 are loaded on graphene 7, and graphene 7 is well dispersed and in a flat state; and the manganese dioxide particles 8 are loaded on the graphene 7, the content of the manganese dioxide is 40 percent and is higher than the optimal 10-30 percent, and the consistency of the particle size of the manganese dioxide is low.
The free radical quenching agent is prepared into slurry through mixing the free radical quenching agent and a hydroalcoholic solution, free radical quenching layers are sprayed on two sides of a proton membrane through a spraying method, the thickness is 500nm, a membrane electrode is prepared, the initial output voltage and the attenuation condition after 200 hours are tested, and the data are shown in table 1.
Example 2:
10g of carbon nanotubes are treated in 2mol/L nitric acid at 130 ℃ for 1h, then washed, filtered and dried at 80 ℃ overnight. Weighing 1g of the carbon nano tube subjected to acid treatment and 0.58g of cerium nitrate, uniformly dispersing in 500ml of hydroalcoholic solution, adding 30ml of ammonia water, and treating at 160 ℃ for 3 hours to prepare 20 wt% CeO2Carbon nanotubes, i.e. free radical quenchers.
FIG. 5 is a transmission electron microscope picture of the present embodiment, in which cerium oxide particles 10 are loaded on carbon nanotubes 9, and the carbon nanotubes 9 are well dispersed and have no obvious agglomeration phenomenon; the cerium dioxide particles 10 are loaded on the carbon nano tubes 9, the content of the cerium dioxide is 20%, the content is moderate, the distribution is uniform, and the consistency of the particle size is good.
Preparing the free radical quenching agent into slurry, spraying free radical quenching layers on two sides of a proton membrane by a spraying method, wherein the thickness of the free radical quenching layers is 500nm, preparing a membrane electrode, and testing the initial output voltage and the attenuation condition after 200 hours, wherein the data are shown in table 1.
Example 3:
the remaining conditions of example 2 were unchanged, and the thickness of the quenching layer was varied only, and a 1 μm radical quenching layer was prepared by spraying.
Example 4:
the remaining conditions of example 2 were unchanged, and the thickness of the quenching layer was varied only, and 2 μm of the radical quenching layer was prepared by spraying.
Example 5:
10gthe carbon nano tube is treated in 3mol/L nitric acid at 120 ℃ for 1h, and then is washed, filtered and dried at 70 ℃ overnight. Weighing the above 2g of acid-treated carbon nanotube and 3.52g of cerium chloride, uniformly dispersing in 800ml of hydroalcoholic solution, adding 40ml of ammonia water, and treating at 160 ℃ for 2h to obtain 50 wt% CeO2A carbon nanotube.
Preparing the quenching agent into slurry, spraying free radical quenching layers on two sides of a proton membrane by a spraying method, wherein the thickness of the free radical quenching layers is 1 mu m, preparing a membrane electrode, and testing the initial output voltage and the attenuation condition after 200 hours, wherein the data are shown in table 1.
Example 6:
the rest conditions of the example 5 are not changed, only the thickness of the quenching layer is changed, and the free radical quenching layer with the thickness of 500nm is prepared by spraying.
Example 7:
the remaining conditions of example 5 were unchanged, and the thickness of the quenching layer was varied only, and 2 μm of the radical quenching layer was prepared by spraying.
Comparative example 1:
20 wt% of CeO2the/CNT is added into a cathode-anode catalytic layer, and a cathode catalytic layer is CeO2The loading amount of (A) is 0.05mg/cm2Anode catalyst layer CeO2Loading amount of 0.02mg/cm2And then preparing a membrane electrode, and testing the initial output voltage and the attenuation condition after 200 hours, wherein the data are shown in table 1.
Comparative example 2:
20 wt% of CeO2Adding graphene into cathode and anode catalyst layers, and adding CeO into the cathode catalyst layer2The loading amount of (A) is 0.05mg/cm2Anode catalyst layer CeO2The loading amount of (A) is 0.02mg/cm2And then preparing a membrane electrode, and testing the initial output voltage and the attenuation condition after 200 hours, wherein the data are shown in table 1.
Comparative example 3:
as commercial CeO2For example, CeO2The particles are added into a cathode-anode catalyst layer, and the cathode catalyst layer is CeO2The loading amount of (A) is 0.05mg/cm2The loading capacity of the anode catalyst layer CeO2 is 0.02mg/cm2. Then preparing a membrane electrode, testing the initial output voltage and the attenuation condition after 200 hours,the data are shown in Table 1.
Comparative example 4:
taking a commercial 15 μm proton membrane as an example, the membrane electrode was tested for initial output voltage and decay after 200h without adding any radical quencher, and the data are shown in table 1.
Taking the membrane electrodes of examples 1-7 and comparative examples 1-4, introducing hydrogen gas into the anode, introducing air into the cathode, controlling the outlet pressure of the cathode and the anode at 150kPa (gauge pressure), the cell temperature at 80 ℃, the relative humidity of the cathode and the anode at 50%, the gas metering ratio at 5, and the current density at 200mA/cm2The endurance test time was 200 h.
The following table shows durability test data of the membrane electrodes prepared in each example and comparative example.
TABLE 1
| Membrane electrode | Initial voltage (V) | Voltage after 200h (V) | Pressure drop (mV) |
| Example 1 | 0.946 | 0.928 | 18 |
| Example 2 | 0.948 | 0.932 | 16 |
| Example 3 | 0.952 | 0.934 | 18 |
| Example 4 | 0.945 | 0.935 | 10 |
| Example 5 | 0.948 | 0.926 | 22 |
| Example 6 | 0.951 | 0.931 | 20 |
| Example 7 | 0.950 | 0.935 | 15 |
| Comparative example 1 | 0.932 | 0.890 | 42 |
| Comparative example 2 | 0.929 | 0.871 | 58 |
| Comparative example 3 | 0.905 | 0.802 | 103 |
| Comparative example 4 | 0.958 | 0.742 | 216 |
As shown in the above table and FIG. 1, it can be seen that the decay voltage of the radical quencher of the present invention is controlled to about 20mV in the membrane electrode durability test. Whereas commercial free radical quenchers, the membrane electrode voltage decayed more than 200 mV. The above description is only a preferred embodiment of the present invention, and should not be construed as limiting the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. The free radical quencher is characterized by comprising a carrier and an active substance, wherein the carrier is carbon black, carbon nano tube or graphene, and the active substance is CeO2、MnO2、WO3、Fe3O4、RuO2The free radical quenching agent comprises one or more of a noble metal phosphate compound, a metal phosphate compound or a metal fluoride, and the content of active substances in the free radical quenching agent is 10-60 wt%.
2. The radical quencher according to claim 1, wherein the active species of the radical quencher is nano-particles having a particle size of 1-50 nm.
3. The radical quencher according to claim 1 or 2, wherein the carrier is carbon nanotubes or graphene; the active material being CeO2Or MnO2(ii) a The content of active substances in the free radical quencher is 10-30 wt%.
4. A method for preparing a free radical quencher, the method comprising:
carrying out oxidation treatment on the carrier;
by the liquid phase synthesis method, an alkaline agent deposits an active substance precursor on the carrier, and the active substance precursor is reduced or oxidized again to load an active substance on the carrier.
5. The method according to claim 4,
treating the carrier in 1-5mol/L oxidant at 50-130 deg.c;
and drying the treated carrier, mixing the dried carrier with an active substance precursor, adding a hydroalcoholic solution and an alkaline reagent, and reacting for 2-10h at the temperature of 120-180 ℃ to generate the free radical quencher.
6. The preparation method according to claim 5, wherein the oxidizing agent is any one of nitric acid, sulfuric acid, perchloric acid, hydrogen peroxide, potassium dichromate or potassium permanganate;
the mass ratio of the active substance/(active substance + carrier) is 10-60 wt%; the alkaline reagent is any one of sodium hydroxide, potassium hydroxide or ammonia water; the volume ratio of the water, the alcohol and the alkaline reagent is (40-60): (20-30): (1-5).
7. The method according to claim 5 or 6, wherein the oxidizing agent is any one of nitric acid, sulfuric acid, or hydrogen peroxide.
8. The application of the free radical quencher in the membrane electrode is characterized in that a reaction layer of the free radical quencher is arranged on the surface of a proton exchange membrane of the membrane electrode and is used for blocking free radicals from attacking and corroding groups on perfluorosulfonic acid of the proton exchange membrane.
9. The use of claim 8, wherein the radical quencher is sprayed on both sides of the proton exchange membrane: preparing slurry by a free radical quenching agent, and then spraying by adopting a spraying process.
10. The use according to claim 9, wherein the spray coating of the free radical quencher has a thickness of from 200nm to 2 μm.
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