CN113161557A - Application of sulfonated polyaryletherketone as binder in membrane electrode of proton exchange membrane fuel cell, membrane electrode and preparation method - Google Patents
Application of sulfonated polyaryletherketone as binder in membrane electrode of proton exchange membrane fuel cell, membrane electrode and preparation method Download PDFInfo
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- CN113161557A CN113161557A CN202110256080.7A CN202110256080A CN113161557A CN 113161557 A CN113161557 A CN 113161557A CN 202110256080 A CN202110256080 A CN 202110256080A CN 113161557 A CN113161557 A CN 113161557A
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- sulfonated polyaryletherketone
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- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 146
- 239000012528 membrane Substances 0.000 title claims abstract description 110
- 239000000446 fuel Substances 0.000 title claims abstract description 73
- 239000011230 binding agent Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 84
- 239000002904 solvent Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 239000000178 monomer Substances 0.000 claims description 50
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 238000009792 diffusion process Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 238000006277 sulfonation reaction Methods 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 10
- 239000002737 fuel gas Substances 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 description 32
- 239000000243 solution Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 23
- 159000000000 sodium salts Chemical class 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- 230000010287 polarization Effects 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 229920000557 Nafion® Polymers 0.000 description 11
- 238000006073 displacement reaction Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 6
- 150000008041 alkali metal carbonates Chemical class 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XSTITJMSUGCZDH-UHFFFAOYSA-N 4-(4-hydroxy-2,6-dimethylphenyl)-3,5-dimethylphenol Chemical group CC1=CC(O)=CC(C)=C1C1=C(C)C=C(O)C=C1C XSTITJMSUGCZDH-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical group 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001502129 Mullus Species 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Images
Classifications
-
- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
-
- 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
- H01M4/8828—Coating with slurry or ink
-
- 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 belongs to the technical field of fuel cells, and particularly relates to application of sulfonated polyaryletherketone as a binder in a membrane electrode of a proton exchange membrane fuel cell. In the invention, the sulfonated polyaryletherketone as the binder can be completely dissolved in the low-boiling-point solvent, so that the problem that the catalyst is poisoned due to the fact that the high-boiling-point solvent is remained in a large amount in the catalyst layer due to the difficulty in removing the high-boiling-point solvent after the binder is dissolved in the high-boiling-point solvent is avoided; the sulfonated polyaryletherketone is used as a binder of the catalyst layer, so that the interface compatibility of the catalyst layer and a proton exchange membrane is improved, a good three-phase reaction interface of fuel gas, water and a catalyst can be constructed, the proton transfer, the substance transportation and the charge transfer in the catalyst layer are smoothly carried out, the proton conductivity of the sulfonated polyaryletherketone is good, the efficient transfer of protons in the catalyst layer of the proton exchange membrane fuel cell is ensured, and the power of the proton exchange membrane fuel cell is greatly improved.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to an application of sulfonated polyaryletherketone as a binder in a membrane electrode of a proton exchange membrane fuel cell, a membrane electrode and a preparation method.
Background
The proton exchange membrane fuel cell has the advantages of high energy efficiency and energy density, small volume and weight, short cold start time and safe and reliable operation, can avoid electrolyte corrosion because the used electrolyte membrane is solid, and is widely applied to industries such as automobile industry, energy power generation, ship industry, aerospace, household power supply and the like.
The core component of the proton exchange membrane fuel cell is a membrane electrode therein, which mainly comprises a proton exchange membrane, a catalyst layer and a gas diffusion layer. The gas catalyst layer contains a binder, the binder is contacted with the catalyst, the electrode carrier, the proton exchange membrane and gas and water entering the membrane electrode, protons are transferred from the inside of the anode catalyst layer to the cathode catalyst layer/proton exchange membrane interface and from the membrane/cathode catalyst layer interface to the inside of the cathode catalyst layer, and the proton transmission required by the oxygen reduction reaction and the hydrogen oxidation reaction in the membrane electrode is directly influenced; meanwhile, the adhesive enables the catalyst layer and the proton exchange membrane to be tightly combined, and the interface resistance between the catalyst layer and the proton exchange membrane is influenced. Therefore, the excellent binder in the proton exchange membrane fuel cell needs to satisfy the following requirements: has higher proton conductivity and good interface compatibility with a proton exchange membrane.
In the existing binders, the perfluorosulfonic acid binder has high proton conductivity, but the compatibility of the binder and a proton exchange membrane interface is poor; the hydrocarbon compound binder can meet the problem of good interface compatibility of the binder and a proton exchange membrane, but has low proton conductivity and small electrochemical active area. In view of the structure and advantages of both perfluorosulfonic acid binders and hydrocarbon binders, researchers have proposed sulfonated aromatic hydrocarbon binders, but most sulfonated aromatic hydrocarbons are soluble only in high boiling solvents and are insoluble in the low boiling water/alcohol mixture solvents widely used in binder dispersion systems. In the preparation process of the electrode, the solvent with high boiling point is difficult to completely remove, so that more solvent residues are adsorbed on the surface of the catalyst, the electrochemical active area of the electrode is reduced, and the acquisition of good electrochemical performance of the proton exchange membrane fuel cell is not facilitated.
Disclosure of Invention
In view of the above, the present invention provides an application of sulfonated polyaryletherketone as a binder in a membrane electrode of a proton exchange membrane fuel cell, where the sulfonated polyaryletherketone is applied as a binder in a proton exchange membrane fuel cell, and can achieve good dissolution and dispersion of the binder in a low boiling point solvent, so as to be beneficial to thoroughly removing the low boiling point solvent attached to the surface of a catalyst when the binder is mixed with the catalyst to prepare a cell electrode, and improve the electrochemical performance of the proton exchange membrane fuel cell.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides an application of sulfonated polyaryletherketone as a binder in a proton exchange membrane fuel cell, wherein monomer units of the sulfonated polyaryletherketone are a first monomer unit and a second monomer unit, and the first monomer unit has a structure shown in a formula I:
the second monomer unit has a structure represented by formula II:
the molar ratio of the first monomer unit to the second monomer unit is not less than 1.
Preferably, the sulfonation degree of the sulfonated polyaryletherketone is 0.5-1.5.
Preferably, the weight average molecular weight of the sulfonated polyaryletherketone is 40000-140000 g/mol.
Preferably, the proton conductivity of the sulfonated polyaryletherketone at 25 ℃ is more than or equal to 50 mS/cm.
Preferably, the proton exchange membrane fuel cell comprises a direct methanol fuel cell or a hydrogen fuel cell.
Preferably, the sulfonated polyaryletherketone is positioned in a catalyst layer of the membrane electrode.
The invention also provides a membrane electrode, which comprises a proton exchange membrane, a first catalyst layer and a second catalyst layer on two sides of the proton exchange membrane, and a first gas diffusion layer on the outer side of the first catalyst layer and a second gas diffusion layer on the outer side of the second catalyst layer, wherein the binders in the first catalyst layer and the second catalyst layer are sulfonated polyaryletherketone, the monomer units of the sulfonated polyaryletherketone are a first monomer unit and a second monomer unit, and the first monomer unit has a structure shown in formula I:
the second monomer unit has a structure represented by formula II:
the molar ratio of the first monomer unit to the second monomer unit is not less than 1.
The invention also provides a preparation method of the membrane electrode in the technical scheme, which comprises the following steps:
mixing a sulfonated polyaryletherketone solution and a catalyst to obtain catalyst slurry, wherein a solvent in the sulfonated polyaryletherketone solution is a low-boiling-point solvent, and the boiling point of the low-boiling-point solvent is lower than 100 ℃;
coating the catalyst slurry on two sides of a proton exchange membrane, removing a solvent in a sulfonated polyaryletherketone solution, and forming a first catalyst layer and a second catalyst layer on two sides of the proton exchange membrane to obtain a primary membrane electrode;
and respectively compounding a first gas diffusion layer and a second gas diffusion layer on two sides of the primary membrane electrode to obtain the membrane electrode.
Preferably, the low-boiling-point solvent is an isopropanol aqueous solution, and the mass ratio of isopropanol to water in the isopropanol aqueous solution is (1-2): 1; the concentration of the sulfonated polyaryletherketone solution is 3-5 wt.%.
Preferably, the mass ratio of the sulfonated polyaryletherketone to the catalyst in the catalyst slurry is 2: (6-15).
The invention provides an application of sulfonated polyaryletherketone as a binder in a membrane electrode of a proton exchange membrane fuel cell, wherein monomer units of the sulfonated polyaryletherketone are a first monomer unit and a second monomer unit, and the first monomer unit has a structure shown in a formula I:
the second monomer unit has a structure represented by formula II:
the molar ratio of the first monomer unit to the second monomer unit is not less than 1.
In the invention, the sulfonated polyaryletherketone as the binder can be completely dissolved in the low-boiling-point solvent, so that the problem that the catalyst is poisoned due to the fact that the high-boiling-point solvent is remained in a large amount in the catalyst layer due to the difficulty in removing the high-boiling-point solvent after the binder is dissolved in the high-boiling-point solvent is avoided; the sulfonated polyaryletherketone is used as a binder of the catalyst layer, so that the interface compatibility of the catalyst layer and a proton exchange membrane is improved, a good three-phase reaction interface of fuel gas, water and a catalyst can be constructed, the proton transfer, the substance transportation and the charge transfer in the catalyst layer are smoothly carried out, the proton conductivity of the sulfonated polyaryletherketone is good, the efficient transfer of protons in the catalyst layer of the proton exchange membrane fuel cell is ensured, and the power of the proton exchange membrane fuel cell is greatly improved.
The test result of the embodiment shows that the sulfonated polyaryletherketone can be completely dissolved in an isopropanol aqueous solution as a binder, the proton conductivity of the sulfonated polyaryletherketone is 120-280 mS/cm and is far higher than that of a commercialized Nafion binder at the same temperature; the maximum power density of the direct methanol fuel cell and the hydrogen fuel cell obtained by taking the sulfonated polyaryletherketone as the binder is higher than that of the direct methanol fuel cell and the hydrogen fuel cell taking Nafion as the binder.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of sulfonated polyaryletherketone obtained in example 1 and example 2;
FIG. 2 is a view showing an aqueous isopropanol solution of the sulfonated polyaryletherketone obtained in example 1 and example 2;
FIG. 3 is a graph showing proton conductivity results of the sulfonated polyaryletherketone obtained in example 1 at different temperatures;
FIG. 4 is a graph showing proton conductivity results of the sulfonated polyaryletherketone obtained in example 2 at different temperatures;
FIG. 5 is a graph showing the results of proton conductivity at different temperatures for Nafion of comparative example 1;
fig. 6 is a polarization graph of direct methanol fuel cells obtained in application example 1 and comparative application example 1;
fig. 7 is a polarization graph of the hydrogen fuel cells obtained in application example 2 and comparative application example 2;
FIG. 8 is a polarization diagram of direct methanol fuel cells obtained in application example 3 and comparative application example 1;
fig. 9 is a graph showing polarization curves of the hydrogen fuel cells obtained in application example 4 and comparative application example 2.
Detailed Description
The invention provides an application of sulfonated polyaryletherketone as a binder in a membrane electrode of a proton exchange membrane fuel cell, wherein monomer units of the sulfonated polyaryletherketone are a first monomer unit and a second monomer unit, and the first monomer unit has a structure shown in a formula I:
the second monomer unit has a structure represented by formula II:
the molar ratio of the first monomer unit to the second monomer unit is not less than 1.
In the invention, the sulfonation degree of the sulfonated polyaryletherketone is preferably 0.5-1.5, more preferably 0.6-1.4, and still more preferably 0.7-1.3.
In the invention, the weight average molecular weight of the sulfonated polyaryletherketone is preferably 40000-140000 g/mol, more preferably 60000-140000 g/mol, and even more preferably 70000-110000 g/mol.
In the present invention, the proton conductivity of the sulfonated polyaryletherketone at 25 ℃ is preferably not less than 50 mS/cm.
In the present invention, the sulfonated polyaryletherketone is preferably prepared by the method I or the method II.
In the present invention, the method I preferably comprises the steps of:
mixing 4,4 '-difluorobenzophenone, 4' -difluorobenzophenone-3, 3 '-disodium disulfonate, 3',5,5 '-tetramethyl-4, 4' -dihydroxybiphenyl, sulfolane and alkali carbonate, and sequentially carrying out a first polymerization reaction and a second polymerization reaction to obtain sulfonated polyaryletherketone sodium salt;
and mixing the sodium salt of the sulfonated polyaryletherketone with a sulfuric acid aqueous solution, and carrying out a displacement reaction to obtain a solid substance, namely the sulfonated polyaryletherketone.
The sulfonated poly (aryl ether ketone) sodium salt is prepared by mixing 4,4 '-difluorobenzophenone, 4' -difluorobenzophenone-3, 3 '-disodium disulfonate, 3',5,5 '-tetramethyl-4, 4' -dihydroxybiphenyl, sulfolane and alkali carbonate, and sequentially carrying out a first polymerization reaction and a second polymerization reaction.
In the present invention, the alkali metal carbonate is preferably anhydrous potassium carbonate.
In the present invention, the mass ratio of the 4,4 '-difluorobenzophenone, the disodium 4,4' -difluorobenzophenone-3, 3 '-disulfonate, the 3,3',5,5 '-tetramethyl-4, 4' -dihydroxybiphenyl, the sulfolane, and the alkali metal carbonate is preferably 4.3641: 12.6687: 12.1152: 87.44: 7.59. in the present invention, the temperature of the first polymerization reaction is preferably 140 ℃ and the time is preferably 3 hours; the temperature of the second polymerization reaction is preferably 210 ℃ and the time is preferably 3 hours. In the present invention, the temperature of the first polymerization reaction is preferably obtained by raising the temperature at normal temperature; the heating rate is preferably 1 to 1.5 ℃/min, and more preferably 1.2 to 1.5 ℃/min. In the present invention, the temperature of the second polymerization reaction is preferably obtained by raising the temperature of the first polymerization reaction; in the present invention, the rate of temperature increase from the temperature of the first polymerization reaction to the temperature of the second polymerization reaction is preferably 0.3 to 0.5 ℃/min, more preferably 0.3 to 0.4 ℃/min. In the present invention, the first polymerization reaction and the second polymerization reaction are preferably carried out under a shielding gas condition; the shielding gas is preferably nitrogen. In the invention, the first polymerization reaction substitutes phenol into a salt form, which is called salt formation reaction; the second polymerization reaction is a polycondensation reaction.
After the sodium salt of the sulfonated polyaryletherketone is obtained, the sodium salt of the sulfonated polyaryletherketone and a sulfuric acid aqueous solution are mixed for a displacement reaction, and the obtained solid substance is the sulfonated polyaryletherketone.
In the present invention, the concentration of the aqueous sulfuric acid solution is preferably 1 mol/L. The relative amounts of the sodium salt of sulfonated polyaryletherketone and the aqueous solution of sulfuric acid and the operation of the replacement reaction are not particularly limited, so that the sodium salt of sulfonated polyaryletherketone can be fully subjected to H replacement to obtain the sulfonated polyaryletherketone.
In the present invention, after the displacement reaction, the present invention preferably further comprises performing solid-liquid separation on a product system obtained by the displacement reaction, and sequentially grinding, washing and drying the obtained solid substance to obtain the sulfonated polyaryletherketone. The grinding is not particularly limited in the invention, and the method is based on obtaining fine sulfonated polyaryletherketone; the water washing is not specially limited in the invention, and the aim is to remove impurities on the surface of the sulfonated polyaryletherketone. In the invention, the drying temperature is preferably 60-65 ℃, and more preferably 61-64 ℃; the time is preferably 24 to 36 hours, and more preferably 28 to 34 hours.
In the present invention, the process II preferably comprises the steps of:
mixing 4,4 '-difluorobenzophenone, 3',5,5 '-tetramethyl-4, 4' -dihydroxybiphenyl, sulfolane and alkali metal carbonate, and sequentially carrying out a polymerization reaction and b polymerization reaction to obtain polyaryletherketone;
mixing the polyaryletherketone and concentrated sulfuric acid, carrying out a displacement reaction, carrying out solid-liquid separation after cooling the obtained reaction system with ice water, placing the obtained solid substance in distilled water for pH value adjustment, and sequentially washing and drying the obtained alkalescent sulfonated polyaryletherketone sodium salt to obtain a sulfonated polyaryletherketone sodium salt;
and mixing the sodium salt of the sulfonated polyaryletherketone with a sulfuric acid aqueous solution, and carrying out a displacement reaction to obtain a solid substance, namely the sulfonated polyaryletherketone.
The method comprises the steps of mixing 4,4 '-difluorobenzophenone, 3',5,5 '-tetramethyl-4, 4' -dihydroxybiphenyl, sulfolane and alkali metal carbonate, and sequentially carrying out a polymerization reaction and b polymerization reaction to obtain the polyaryletherketone.
In the present invention, the alkali metal carbonate is preferably anhydrous potassium carbonate.
In the present invention, the mass ratio of the 4,4 '-difluorobenzophenone, the 3,3',5,5 '-tetramethyl-4, 4' -dihydroxybiphenyl, the sulfolane and the alkali metal carbonate is preferably 10.9103: 12.1152: 69.07: 7.59. in the present invention, the temperature of the polymerization reaction is preferably 140 ℃, and the time is preferably 3 h; the polymerization reaction temperature is preferably 210 ℃ and the time is preferably 3 h. In the invention, the temperature of the polymerization reaction a is preferably obtained by raising the temperature at normal temperature; the heating rate is preferably 1-2 ℃/min, and more preferably 1.2-1.8 ℃/min. In the present invention, the temperature of the b polymerization reaction is preferably obtained by raising the temperature of the a polymerization reaction; in the present invention, the rate of temperature increase from the polymerization reaction temperature of a to the polymerization reaction temperature of b is preferably 0.3 to 0.6 ℃/min, more preferably 0.4 to 0.5 ℃/min. In the present invention, the polymerization reaction a and the polymerization reaction b are preferably carried out under a shielding gas condition; the shielding gas is preferably nitrogen. In the invention, the polymerization reaction a substitutes phenol into a salt form, namely a salt forming reaction; the polymerization reaction is a polycondensation reaction.
After the polymerization reaction of b, the invention preferably carries out solid-liquid separation on a product system obtained by the polymerization reaction of b, and the obtained solid substance is sequentially ground, washed and dried. The invention does not specially limit the grinding to obtain the fine polyaryletherketone; the invention has no special limitation on the water washing, and takes the removal of the surface impurities of the polyaryletherketone as the standard. In the invention, the drying temperature is preferably 70-80 ℃, and more preferably 72-78 ℃; the time is preferably 12 to 18 hours, and more preferably 14 to 16 hours.
After polyaryletherketone is obtained, mixing polyaryletherketone and concentrated sulfuric acid, performing sulfonation reaction, performing solid-liquid separation after cooling the obtained reaction system with ice water, placing the obtained solid substance containing sulfonic groups in distilled water for pH value adjustment, and sequentially washing and drying the obtained alkalescent sulfonated polyaryletherketone sodium salt to obtain the sulfonated polyaryletherketone sodium salt.
In the present invention, the ratio of the mass of the polyaryletherketone to the volume of concentrated sulfuric acid is preferably 10 g: 150 mL. In the present invention, the temperature of the sulfonation reaction is preferably 80 ℃ and the time is preferably 6 hours. In the present invention, the solid-liquid separation is preferably filtration; the filtration is not particularly limited in the present invention, and filtration known to those skilled in the art may be employed. In the present invention, the pH adjusting agent is preferably NaOH. In the invention, the pH value of the weakly alkaline sulfonated polyaryletherketone sodium salt is preferably 8-9. The water washing is not specially limited, and the sodium salt of the sulfonated polyaryletherketone is used as the neutral standard. In the invention, the drying temperature is preferably 60-65 ℃, and more preferably 61-64 ℃; the time is preferably 24 to 36 hours, and more preferably 26 to 34 hours.
After the sodium salt of the sulfonated polyaryletherketone is obtained, the sodium salt of the sulfonated polyaryletherketone is mixed with a sulfuric acid aqueous solution for a displacement reaction, and the obtained solid substance is the sulfonated polyaryletherketone.
In the present invention, the concentration of the aqueous sulfuric acid solution is preferably 1 mol/L. The relative dosage of the sodium salt of sulfonated polyaryletherketone and the aqueous solution of sulfuric acid is not specially limited, and the invention is based on the fact that the sodium salt of sulfonated polyaryletherketone can be fully subjected to H replacement to obtain the sulfonated polyaryletherketone. In the present invention, the temperature of the metathesis reaction is preferably 60 ℃ and the time is preferably 48 hours.
In the invention, the sulfonation degree of the sulfonated polyaryletherketone is adjusted according to the proportion of sulfonated monomers in reactants, or is adjusted and controlled according to the reaction time of the polyaryletherketone and concentrated sulfuric acid.
In the present invention, the proton exchange membrane fuel cell preferably includes a direct methanol fuel cell or a hydrogen fuel cell.
In the present invention, the sulfonated polyaryletherketone is preferably located in the catalyst layer of the membrane electrode.
The invention also provides a membrane electrode, which comprises a proton exchange membrane, a first catalyst layer and a second catalyst layer on two sides of the proton exchange membrane, and a first gas diffusion layer on the outer side of the first catalyst layer and a second gas diffusion layer on the outer side of the second catalyst layer, wherein the binders in the first catalyst layer and the second catalyst layer are sulfonated polyaryletherketone, the monomer units of the sulfonated polyaryletherketone are a first monomer unit and a second monomer unit, and the first monomer unit has a structure shown in formula I:
the second monomer unit has a structure represented by formula II:
the molar ratio of the first monomer unit to the second monomer unit is not less than 1.
The invention also provides a preparation method of the membrane electrode in the technical scheme, which comprises the following steps:
mixing a sulfonated polyaryletherketone solution and a catalyst to obtain catalyst slurry, wherein a solvent in the sulfonated polyaryletherketone solution is a low-boiling-point solvent, and the boiling point of the low-boiling-point solvent is lower than 100 ℃;
coating the catalyst slurry on two sides of a proton exchange membrane, removing a solvent in a sulfonated polyaryletherketone solution, and forming a first catalyst layer and a second catalyst layer on two sides of the proton exchange membrane to obtain a primary membrane electrode;
and respectively compounding a first gas diffusion layer and a second gas diffusion layer on two sides of the primary membrane electrode to obtain the membrane electrode.
The method mixes the sulfonated polyaryletherketone solution with a catalyst to obtain catalyst slurry.
In the invention, the solvent in the sulfonated polyaryletherketone solution is a low-boiling-point solvent, the boiling point of the low-boiling-point solvent is lower than 100 ℃, preferably an isopropanol water solution, and the mass ratio of isopropanol to water in the isopropanol water solution is preferably (1-2): 1, more preferably (1.2 to 1.8): 1. in the invention, the concentration of the sulfonated polyaryletherketone solution is preferably 3-5 wt.%, and more preferably 3.5-5 wt.%.
In the present invention, the catalyst preferably includes a noble metal and carbon. In the present invention, the catalyst preferably comprises Pt/C and PtRu/C. In the present invention, the molar ratio of the noble metal to carbon in the catalyst is preferably 6: 4. in an embodiment of the invention, the catalyst is preferably purchased from the company prolongation mullet. In the invention, the mass ratio of the sulfonated polyaryletherketone to the catalyst in the catalyst slurry is preferably 2: (6-15), more preferably 2: (7-14).
The mixing is not particularly limited in the invention, and the sulfonated polyaryletherketone solution and the catalyst can be uniformly mixed and dispersed.
After the catalyst slurry is obtained, the catalyst slurry is coated on two sides of a proton exchange membrane, a solvent in a sulfonated polyaryletherketone solution is removed, and a first catalyst layer and a second catalyst layer are formed on two sides of the proton exchange membrane to obtain a primary membrane electrode.
The proton exchange membrane is not particularly limited in the present invention, and may be a proton exchange membrane of a proton exchange membrane fuel cell known to those skilled in the art, specifically, a sulfonated polyaryletherketone proton exchange membrane. In the invention, the coating amount of the catalyst slurry on one side surface of the proton exchange membrane is preferably 0.3-2 mg/cm2More preferably 0.5 to 1.5mg/cm2. In the present inventionThe method for removing the solvent in the sulfonated polyaryletherketone solution is preferably a hot-plate drying method.
After the primary membrane electrode is obtained, a first gas diffusion layer and a second gas diffusion layer are respectively compounded on two sides of the primary membrane electrode to obtain the membrane electrode.
The first gas diffusion layer and the second gas diffusion layer are not particularly limited in the present invention, and a gas diffusion layer of a proton exchange membrane fuel cell known to those skilled in the art may be used. The amount of the gas diffusion layer used in the present invention is not particularly limited, and may be any amount known to those skilled in the art. The present invention is not particularly limited to the combination of the gas diffusion layer on both sides of the primary membrane electrode, and the combination well known to those skilled in the art may be used.
In order to further illustrate the present invention, the following examples are provided to describe the application of sulfonated polyaryletherketone as a binder in a membrane electrode of a proton exchange membrane fuel cell, a membrane electrode and a preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
4.3641g of 4,4 '-difluorobenzophenone, 12.6687g of disodium 4,4' -difluorobenzophenone-3, 3 '-disulfonate, 12.1152g of 3,3',5,5 '-tetramethyl-4, 4' -dihydroxybiphenyl, 87.44g of sulfolane and 7.59g of anhydrous potassium carbonate are mixed, heated to 140 ℃ under the protection of nitrogen for reaction for 3 hours, and heated to 210 ℃ at the rate of 0.3 ℃/mn for reaction for 3 hours to obtain the sodium sulfonated polyaryletherketone;
mixing the obtained sodium salt of sulfonated polyaryletherketone with 1mol/L of H2SO4Mixing to perform a displacement reaction on the sodium salt of the sulfonated polyaryletherketone, grinding the solid product after the displacement reaction is finished, repeatedly washing with water, and drying at 60 ℃ for 24 hours to obtain the sulfonated polyaryletherketoneTo said sulfonated polyaryletherketone.
The sulfonated polyaryletherketone obtained in example 1 was subjected to nuclear magnetic resonance test, and the obtained nuclear magnetic resonance hydrogen spectrum is shown in FIG. 1. As can be seen from FIG. 1, the peak a is the peak of the H atom of the benzene ring at the ortho position of the sodium sulfonate group, the peak c is the peak of the H atom of the benzene ring at the para position of the sodium sulfonate group, and the peaks d and e are the peaks of the H atom of the benzene ring at the ortho position of the methyl group, which indicates that the polymer obtained by polymerizing the unit A and the unit B is successfully obtained in this example.
According to formula I, calculating the sulfonation degree of the sulfonated polyaryletherketone by calculating the ratio of the integral areas of peaks corresponding to hydrogen atoms in the nuclear magnetic resonance spectrum of the polymer:
in the formula a, DS refers to the sulfonation degree of sulfonated polyaryletherketone, I (H1) represents the integral area of a peak of a hydrogen atom adjacent to a sulfonic acid group, and I (HR) represents the sum of the integral areas of other peaks of hydrogen atoms on a polymer main chain.
The sulfonation degree of the sulfonated polyaryletherketone obtained in this example was calculated to be 1.2.
Dissolving the sulfonated polyaryletherketone obtained in example 1 in an isopropanol aqueous solution, wherein the mass ratio of isopropanol to water in the isopropanol aqueous solution is 1: 1, obtaining a sulfonated polyaryletherketone solution with a sulfonated polyaryletherketone concentration of 5 wt.%, wherein the macroscopic observation picture of the obtained sulfonated polyaryletherketone solution is shown in figure 2. As can be seen from FIG. 2, the sulfonated polyaryletherketone obtained in this example was uniformly dissolved in an aqueous isopropanol solution.
The proton conductivity of the sulfonated polyaryletherketone obtained in this example was tested at different temperatures, and the proton conductivity results at different temperatures are shown in FIG. 3. As can be seen from FIG. 3, the proton conductivity of the sulfonated polyaryletherketone provided by this embodiment is 120-240 mS/cm at 30-80 ℃.
Example 2
10.9103g of 4,4 '-difluorobenzophenone, 12.1152g of 3,3',5,5 '-tetramethyl-4, 4' -dihydroxybiphenyl, 69.07g of sulfolane and 7.59g of anhydrous potassium carbonate are mixed, the mixture is heated to 140 ℃ under the protection of nitrogen for reaction for 3 hours, the mixture is heated to 210 ℃ at the speed of 0.6 ℃/min for reaction for 3 hours, the obtained product system is poured into water, the obtained solid product is ground, the water is repeatedly washed, and then the mixture is dried at 80 ℃ for 12 hours, so that polyaryletherketone is obtained;
dissolving 10g of polyaryletherketone in 150mL of concentrated sulfuric acid, reacting at 80 ℃ for 6h, pouring a product system into ice water, filtering, adjusting the pH of the solid product to 8 with NaOH, washing with deionized water to be neutral, and drying at 60 ℃ for 24h to obtain sulfonated polyaryletherketone sodium salt with the sulfonation degree of 1.2;
soaking the obtained sodium salt of sulfonated polyaryletherketone in H with the concentration of 1mol/L at the temperature of 60 DEG C2SO4And carrying out a replacement reaction for 48h to obtain the sulfonated polyaryletherketone.
The sulfonated polyaryletherketone obtained in example 2 was subjected to nuclear magnetic resonance test, and the obtained nuclear magnetic resonance hydrogen spectrum is shown in FIG. 1. As can be seen from FIG. 1, this example succeeded in obtaining a polymer obtained by polymerizing the units A and B.
Dissolving the sulfonated polyaryletherketone obtained in example 2 in an isopropanol aqueous solution, wherein the mass ratio of isopropanol to water in the isopropanol aqueous solution is 1: 1, obtaining a sulfonated polyaryletherketone solution with a sulfonated polyaryletherketone concentration of 5 wt.%, wherein the macroscopic observation picture of the obtained sulfonated polyaryletherketone solution is shown in figure 2. As can be seen from FIG. 2, the sulfonated polyaryletherketone obtained in this example was uniformly dissolved in an aqueous isopropanol solution.
The proton conductivity of the sulfonated polyaryletherketone obtained in this example was tested at different temperatures, and the proton conductivity results at different temperatures are shown in FIG. 4. As can be seen from FIG. 4, the proton conductivity of the sulfonated polyaryletherketone provided by the present embodiment is 160-280 mS/cm at 30-80 ℃.
Comparative example 1
Comparative example 1 the binder was Nafion, purchased from Dupont.
The proton conductivity of the comparative example Nafion was tested at different temperatures and the resulting proton conductivity results at different temperatures are shown in figure 5. As can be seen from FIG. 5, the proton conductivity of Nafion provided by the comparative example is 70-140 mS/cm at 30-80 ℃. In addition, as can be seen from the comparison of fig. 3 to fig. 5, the sulfonated polyaryletherketone provided by the present invention has higher proton conductivity than Nafion.
Application example 1
Dissolving the sulfonated polyaryletherketone obtained in example 1 in an isopropanol water solution (the mass ratio of isopropanol to water is 1: 1) to obtain a sulfonated polyaryletherketone solution with the sulfonated polyaryletherketone concentration of 5 wt.%;
mixing 0.02g of sulfonated polyaryletherketone solution and 0.15g of Pt/C catalyst to obtain catalyst slurry;
coating the catalyst slurry on two sides of a sulfonated polyaryletherketone proton exchange membrane, and removing a solvent to obtain a primary membrane electrode formed by compounding the proton exchange membrane and catalyst layers on the two sides;
and respectively compounding gas diffusion layers of PTFE (polytetrafluoroethylene) treated carbon paper on two sides of the primary membrane electrode to obtain the membrane electrode, wherein the thickness of the PTFE treated carbon paper is 32 mm.
And 2M methanol is used as fuel gas, and the membrane electrode obtained in the application example 1 is adopted to assemble the direct methanol fuel cell.
The polarization curves of the resulting direct methanol fuel cells were tested at 75 deg.c and the polarization curves of the resulting direct methanol fuel cells are shown in fig. 6. As can be seen from FIG. 6, the maximum power density of the obtained direct methanol fuel cell using the sulfonated polyaryletherketone provided in example 1 of the present invention as a binder is 92 mW/cm.
Application example 2
According to the method of application example 1, the sulfonated polyaryletherketone obtained in example 1 is used as a binder to obtain a membrane electrode;
and (3) assembling the membrane electrode obtained in the application example 2 by using high-purity hydrogen as fuel gas to obtain the hydrogen-fuel battery.
The resulting polarization curves of the hydrogen fuel cells were tested at 75 deg.c and the resulting polarization curves of the hydrogen fuel cells are shown in fig. 7. As can be seen from FIG. 7, the maximum power density of the resulting hydrogen fuel cell using the sulfonated polyaryletherketone provided in example 1 of the present invention as a binder was 515 mW/cm.
Application example 3
According to the method of application example 1, the sulfonated polyaryletherketone obtained in example 2 is used as a binder to obtain a membrane electrode;
and 2M methanol is used as fuel gas, and the membrane electrode obtained in the application example 3 is adopted to assemble the direct methanol fuel cell.
The polarization curves of the resulting direct methanol fuel cells were tested at 75 deg.c and the polarization curves of the resulting direct methanol fuel cells are shown in fig. 8. As can be seen from FIG. 8, the maximum power density of the obtained direct methanol fuel cell using the sulfonated polyaryletherketone provided in example 2 of the present invention as a binder is 87 mW/cm.
Application example 4
According to the method of application example 1, the sulfonated polyaryletherketone obtained in example 2 is used as a binder to obtain a membrane electrode;
and (3) assembling the membrane electrode obtained in the application example 4 by using high-purity hydrogen as fuel gas to obtain the hydrogen fuel cell.
The resulting polarization curves of the hydrogen fuel cells were tested at 75 deg.c and the resulting polarization curves of the hydrogen fuel cells are shown in fig. 9. As can be seen from FIG. 9, the maximum power density of the resulting hydrogen fuel cell using the sulfonated polyaryletherketone provided in example 2 of the present invention as a binder was 487 mW/cm.
Comparative application example 1
According to the method of application example 1, the Nafion of comparative example 1 is used as a binder to obtain a membrane electrode;
and 2M methanol is used as fuel gas, and the membrane electrode obtained in the comparative application example 1 is adopted to assemble the direct methanol fuel cell.
The polarization curves of the resulting direct methanol fuel cells were tested at 75 deg.c and the polarization curves of the resulting direct methanol fuel cells were shown in fig. 6 and 8 (the test results for comparative application example 1 in fig. 6 and 8 were consistent). As can be seen from fig. 6 or 8, the maximum power density of the direct methanol fuel cell obtained using Nafion provided in comparative example 1 of the present invention as a binder was 77 mW/cm. As can be seen from fig. 6, the direct methanol fuel cell obtained in application example 1 has a maximum power density 16% higher than that of the direct methanol fuel cell obtained in comparative application example 1, and is more excellent in electrochemical performance. As can be seen from fig. 8, the maximum power density of the direct methanol fuel cell obtained in application example 3 is 10% higher than that of the direct methanol fuel cell obtained in comparative application example 1, and the electrochemical performance is more excellent.
Comparative application example 2
According to the method of application example 1, the Nafion of comparative example 1 is used as a binder to obtain a membrane electrode;
and (3) assembling the membrane electrode obtained in the comparative application example 2 by using high-purity hydrogen as fuel gas to obtain the hydrogen fuel cell.
The polarization curves of the resulting hydrogen-air fuel cells were tested at 75 deg.c, and the polarization curves of the resulting hydrogen-air fuel cells were shown in fig. 7 and 9 (the test results for comparative application example 2 in fig. 7 and 9 were consistent). As can be seen from fig. 7 or fig. 9, the maximum power density of the resulting hydrogen-air fuel cell was 438mW/cm using Nafion provided in comparative example 1 of the present invention as a binder. As can be seen from fig. 7, the maximum power density of the hydrogen/air fuel cell obtained in application example 2 was higher by 17% than that of the hydrogen/air fuel cell obtained in comparative application example 2, and the electrochemical performance was more excellent. As can be seen from fig. 9, the maximum power density of the hydrogen/air fuel cell obtained in application example 4 was 11% higher than that of the hydrogen/air fuel cell obtained in comparative application example 2, and the electrochemical performance was more excellent.
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. The application of sulfonated polyaryletherketone as a binder in a membrane electrode of a proton exchange membrane fuel cell is characterized in that monomer units of the sulfonated polyaryletherketone are a first monomer unit and a second monomer unit, and the first monomer unit has a structure shown in a formula I:
the second monomer unit has a structure represented by formula II:
the molar ratio of the first monomer unit to the second monomer unit is not less than 1.
2. The use according to claim 1, wherein the sulfonated polyaryletherketone has a degree of sulfonation of 0.5 to 1.5.
3. The use according to claim 1, wherein the sulfonated polyaryletherketone has a weight average molecular weight of 40000 to 140000 g/mol.
4. Use according to claim 1, wherein the sulfonated polyaryletherketone has a proton conductivity at 25 ℃ of more than or equal to 50 mS/cm.
5. The use according to any one of claims 1 to 4, wherein the proton exchange membrane fuel cell comprises a direct methanol fuel cell or a hydrogen fuel cell.
6. The use according to any one of claims 1 to 4, wherein the sulfonated polyaryletherketone is located in a catalyst layer of a membrane electrode.
7. A membrane electrode comprises a proton exchange membrane, a first catalyst layer and a second catalyst layer on two sides of the proton exchange membrane, and a first gas diffusion layer on the outer side of the first catalyst layer and a second gas diffusion layer on the outer side of the second catalyst layer, and is characterized in that a binder in the first catalyst layer and the second catalyst layer is sulfonated polyaryletherketone, monomer units of the sulfonated polyaryletherketone are a first monomer unit and a second monomer unit, and the first monomer unit has a structure shown in a formula I:
the second monomer unit has a structure represented by formula II:
the molar ratio of the first monomer unit to the second monomer unit is not less than 1.
8. The method for producing a membrane electrode according to claim 7, comprising the steps of:
mixing a sulfonated polyaryletherketone solution and a catalyst to obtain catalyst slurry, wherein a solvent in the sulfonated polyaryletherketone solution is a low-boiling-point solvent, and the boiling point of the low-boiling-point solvent is lower than 100 ℃;
coating the catalyst slurry on two sides of a proton exchange membrane, removing a solvent in a sulfonated polyaryletherketone solution, and forming a first catalyst layer and a second catalyst layer on two sides of the proton exchange membrane to obtain a primary membrane electrode;
and respectively compounding a first gas diffusion layer and a second gas diffusion layer on two sides of the primary membrane electrode to obtain the membrane electrode.
9. The preparation method according to claim 8, wherein the low-boiling-point solvent is an aqueous isopropanol solution, and the mass ratio of isopropanol to water in the aqueous isopropanol solution is (1-2): 1; the concentration of the sulfonated polyaryletherketone solution is 3-5 wt.%.
10. The preparation method of claim 8, wherein the mass ratio of the sulfonated polyaryletherketone to the catalyst in the catalyst slurry is 2: (6-15).
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Application publication date: 20210723 |
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