CN102146162B - Preparation method and application of polybenzimidazole binder - Google Patents
Preparation method and application of polybenzimidazole binder Download PDFInfo
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- CN102146162B CN102146162B CN2011100411931A CN201110041193A CN102146162B CN 102146162 B CN102146162 B CN 102146162B CN 2011100411931 A CN2011100411931 A CN 2011100411931A CN 201110041193 A CN201110041193 A CN 201110041193A CN 102146162 B CN102146162 B CN 102146162B
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- polybenzimidazole
- sticker
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- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 61
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011230 binding agent Substances 0.000 title abstract 5
- 239000000446 fuel Substances 0.000 claims abstract description 30
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 33
- 238000009792 diffusion process Methods 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 210000000170 cell membrane Anatomy 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000011267 electrode slurry Substances 0.000 claims description 11
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical group C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 2
- 239000000010 aprotic solvent Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 229920005596 polymer binder Polymers 0.000 abstract 1
- 239000002491 polymer binding agent Substances 0.000 abstract 1
- 238000010248 power generation Methods 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- INAAIJLSXJJHOZ-UHFFFAOYSA-N pibenzimol Chemical compound C1CN(C)CCN1C1=CC=C(N=C(N2)C=3C=C4NC(=NC4=CC=3)C=3C=CC(O)=CC=3)C2=C1 INAAIJLSXJJHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- -1 polyphenylene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
Classifications
-
- 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 preparation method and application of a polybenzimidazole binder. The polybenzimidazole binder with the molecular weight of 5,000 to 16,000 is prepared from monomers of 3,3',4,4'-4 aminobphenyl and isophthalic acid by polycondensation in a molar ratio of 1:1.02 to 1:1.06. The polymer binder is easy to dissolve into numerous aprotic solvents and has high bonding performance. The defects of poor solubility of high molecular weight polybenzimidazole and poor bonding performance of low molecular weight polybenzimidazole are overcome. When the binder is used for preparing a membrane electrode of a fuel cell, a complex solubilizer is not required in the process, so that the preparation process is simplified. The membrane electrode prepared by the polybenzimidazole binder can be used for power generation of the hydrogen oxygen and hydrogen air fuel cells under the condition without humidification at a temperature of higher than 100 DEG C. At a temperature of 160 DEG C and under the condition without humidification, the hydrogen and oxygen fuel cell has the maximum power density of 366mW/cm2 (976mA/cm2, 0.375V).
Description
Technical field
The present invention relates to a kind of preparation method and application of sticker, particularly a kind of preparation method of polybenzimidazole sticker and application, the polybenzimidazole sticker is used for fuel cell membrane electrode.
Background technology
Polybenzimidazole is one type of high performance material, has high resistance toheat, excellent mechanical property, fabulous chemicalstability, good dielectric properties and spinning properties, in fields such as aerospace, microelectronics, has obtained using widely.In recent years, the researchist finds that phosphate-doped polybenzimidazole membrane is a kind of polymer dielectric film with excellent anti-oxidation characteristics and thermostability, still can keep than high proton conductivity and certain mechanical strength to 250 ℃ of high temperature.This type material has the potential application prospect in novel low-cost high temperature polymer electrolyte membrane type fuel cell field, therefore receives extensive concern.The electrolytical composition of polybenzimidazole of main research is for gathering [2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] at present, and molecular weight is higher than 20000, and structural formula is following:
In the membrane electrode with phosphate-doped polybenzimidazole dielectric film preparation, the sticker of catalyst layer can adopt multiple polymers at present.
The report that 2000 the 45th volumes of 447 pages of ECS Transactions 2006 the 3rd volumes and Electrochimica Acta are 4219 pages adopts tetrafluoroethylene as sticker, and the former also adopts ethylene-acrylic acid copolymer as sticker.In this catalyst layer, dipping perhaps is penetrated into the free phosphoric acid proton conducting of catalyst layer, catalyzer and carrier conduction electronics, and the catalyst layer height is hydrophobic, and reactant gases gets into the active sites on electrode interior contact catalyst surface easily, thereby constitutes three phase boundary.But because tetrafluoroethylene and ethylene-acrylic acid copolymer itself are not participated in proton conducting and electronics, big (the about 2-4mg/cm of the platinum carrying capacity that needs in the catalyst layer
2), catalyst utilization is low.
The report that 2006 the 280th volumes of 1410 pages of Macromolecular Rapid Communications 2004 the 25th volumes and Journal of MembraneScience are 351 pages adopts perfluorinated sulfonic acid compounds Nafion as sticker.In this catalyst layer, the Nafion of hydration and the common proton conducting of free phosphoric acid that is penetrated into catalyst layer.But do not have the humidification long-play at 100 ℃ when fuel cell, especially more than 120 ℃ the time, dehydration can take place in Nafion, and the proton electricity is led decay, and fuel battery performance significantly descends.
Journal of Power Sources rolled up 27 pages in 2006 the 160th; The report that 2006 the 31st volumes of 193 pages of 1996 the 41st volumes of 278 pages of Electrochimica Acta of Journal of Power Sources 2007 the 172nd volume and International Journal ofHydrogen Energy are 1855 pages adopts high-molecular-weight poly [2; 2 '-(metaphenylene)-5,5 '-bisbenzimidazole] (molecular weight is higher than 20000) as sticker.In this catalyst layer, under the booster action of imidazole ring, dipping or be penetrated into the phosphoric acid proton conducting of catalyst layer, fuel cell can be under no humidified condition more than 100 ℃ long-play.But high-molecular-weight poly [2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] is the polymkeric substance that phenyl ring and aromaticity heterocycle constitute; The molecular chain high degree of rigidity, it is strong to interact between the molecule, makes it poorly soluble; Need add solubility promoter such as lithium chloride etc. during preparation catalyst layer preparation electrode slurries; Need to use hot wash after preparing catalyst layer, remove solubility promoter, process is complicated.[2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] (molecular weight is lower than 3000) solubleness is high although lower molecular weight is gathered, and adhesive property is limited, makes between granules of catalyst, electrode and the dielectric film a little less than the bonding force, is unfavorable for the long-time running of fuel cell.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of polybenzimidazole sticker, this polybenzimidazole sticker molecular weight is 5000-16000, structural formula is following.
This polymkeric substance is dissolved in numerous non-proton type solvents easily and has higher adhesive property.In the phosphate-doped gas diffusion electrode of preparation, add this polybenzimidazole sticker as sticker, need not add solubility promoter, simplified the preparation process.
The preparation method of a kind of polybenzimidazole sticker of the present invention is following:
With 3,3 ', 4,4 '-tetramino biphenyl and m-phthalic acid join in the polyphosphoric acid that contains the 70-90wt% Vanadium Pentoxide in FLAKES; 3,3 ', 4, the mol ratio of 4 '-tetramino biphenyl and m-phthalic acid is 1: 1.02-1: 1.06; 3,3 ', 4, the total mass concentration of 4 '-tetramino biphenyl and m-phthalic acid is 5-20wt%; Under nitrogen protection, in 50-220 ℃ of reaction 5-30 hour, drop to 10-40 ℃ then, precipitating is in water; With alkali neutralization, filter again, be washed till neutrality after, 100 ℃ of vacuum dryings obtain a kind of polybenzimidazole sticker to constant weight, its molecular weight is 5000-16000.
The application method of a kind of polybenzimidazole sticker of the present invention is following:
1 mass parts polybenzimidazole sticker is dissolved in the 100-2000 mass parts organic solvent, adds the platinum C catalyst of 3-20 mass parts again, stir the ultrasonic electrode slurry of making; Electrode slurry is coated on the gas diffusion layers, and 190 ℃ of vacuum dryings obtain gas diffusion electrode to constant weight; The gas diffusion electrode immersion is contained in the ethanolic soln of 15wt% phosphoric acid; Wherein every square centimeter of required volumes of aqueous ethanol that contains 15wt% phosphoric acid of gas diffusion electrode is 1-5ml; Flooded 2-30 minute, and dried to constant weight for 60-80 ℃, obtain phosphate-doped gas diffusion electrode; One side of two phosphate-doped gas diffusion electrode platiniferous C catalysts is placed to high temperature proton exchange film; 100-160 ℃, 1-4MPa hot pressing 1-20 minute; Obtain a kind of polybenzimidazole sticker and be used for fuel cell membrane electrode, wherein polybenzimidazole sticker molecular weight is 5000-16000.
The organic solvent that the present invention uses is DMAC N,N, 1-Methyl-2-Pyrrolidone or DMSO 99.8MIN..
The platinum C catalyst that the present invention uses is the platinum C catalyst that contains 10-60wt% platinum.
The gas diffusion layers that the present invention uses is carbon paper, carbon cloth or the carbon felt of the smooth processing of hydrophobic.
The high temperature proton exchange film that the present invention uses is sulfonation polyimidazole film, sulfonated polyphenyl and imidazoles film, sulfonated polyether benzoglyoxaline film, sulfuric acid doping polybenzimidazole membrane or phosphate-doped polybenzimidazole membrane, and the molecular weight of high temperature proton exchange film is 10000-200000.
Among the preparation method of a kind of polybenzimidazole sticker of the present invention; With mol ratio is 1: 1.02-1: 1.06 3,3 ', 4; 4 '-tetramino biphenyl and m-phthalic acid are that monomer prepares the polybenzimidazole sticker through polycondensation; This gathers [2,2 '-(metaphenylene)-5,5 ' bisbenzimidazole] molecular weight is 5000-16000.This polymkeric substance is dissolved in numerous non-proton type solvents easily and has higher adhesive property, has avoided the shortcoming of high-molecular-weight poly benzo imidazoles poor solubility and low molecular weight polyphenylene and imidazoles bad adhesion.In fuel cell membrane electrode, use this polybenzimidazole sticker, process need not used solubility promoter, has simplified the preparation process.The corresponding fuel cell membrane electrode of the present invention preparation can be higher than be used for hydrogen-oxygen under 100 ℃ of no humidification conditions, hydrogen-air fuel cell generates electricity.Use this membrane electrode, 160 ℃ of hydrogen-oxygen fuel cell temperature, under the no humidified condition, maximum power density 366mW/cm
2(976mA/cm
2, 0.375V).Preparing method's technological process of the present invention is easy, the process good reproducibility.
Description of drawings
Fig. 1 is a kind of polybenzimidazole sticker of embodiment 1 preparation, is used for the polarization performance curve of hydrogen-oxygen fuel cell with the fuel cell membrane electrode of this polybenzimidazole adhesive preparation.
Embodiment
In conjunction with following examples, the present invention is further specified, not delimit the scope of the invention.
The platinum C catalyst that uses in following examples contains the platinum C catalyst of 20wt% platinum or the platinum C catalyst that Johnson Matthey company contains 40wt% platinum as BASF FUEL CELL company.Gas diffusion layers is the carbon cloth type gas diffusion layers of the smooth processing of the BASF FUEL CELL E-TEK ELAT of company LT1200W hydrophobic.To be that the laboratory synthetic is phosphate-doped gather [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film to high temperature proton exchange film, and molecular weight is 40000.
The preparation method of the high temperature proton exchange film that uses in following examples is phosphate-doped to be gathered [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film is following: with 5.0mmol (1.071g) 3; 3 ', 4,4 '-tetramino biphenyl and 5.0mmol (1.291g) 4; 4 '-dicarboxyl phenyl ether joins 20.0g and contains in the polyphosphoric acid of 80% Vanadium Pentoxide in FLAKES, under nitrogen protection, earlier 150 ℃ of reactions 2 hours; Reacted 28 hours down at 190 ℃ afterwards, drop to 10-40 ℃ then, precipitating is in water; With alkali neutralization, filter again, be washed till neutrality after, 100 ℃ of vacuum dryings are gathered [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] to constant weight, its molecular weight is 40000; To gather [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] 2.0g and be dissolved in the DMSO 99.8MIN. of 20.0ml,, gathered [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film in 80 ℃ of casting films; 2.0g being gathered [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film immersed in the 40.0g 85wt% SPA 3 days; 120 ℃ of vacuum dryings are to constant weight; Obtain that high temperature proton exchange film is phosphate-doped to gather [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film.
Embodiment 1
The preparation of polybenzimidazole sticker: with 5.0mmol (1.0710g) 3,3 ', 4; 4 '-tetramino biphenyl and 5.15mmol (0.8556g) m-phthalic acid joins 17.0g and contains in the polyphosphoric acid of 80wt% Vanadium Pentoxide in FLAKES; Under nitrogen protection, 150 ℃ of reactions 2 hours, reacted 28 hours down at 190 ℃ afterwards earlier; Drop to 25 ℃ then, precipitating is in water; With alkali neutralization, filter again, be washed till neutrality after, 100 ℃ of vacuum dryings obtain the polybenzimidazole sticker to constant weight, its molecular weight is 9400.
The polybenzimidazole sticker is used for the preparation of fuel cell membrane electrode: the polybenzimidazole sticker of 0.0010g is dissolved in 2.0g N; In the N-N,N-DIMETHYLACETAMIDE, add 0.0200g 40wt% platinum C catalyst again, stirred 24 hours; Ultrasonic 20 minutes, make electrode slurry; Electrode slurry is coated on two 2.5cm * 2.5cm gas diffusion layers, and 190 ℃ of vacuum dryings obtain gas diffusion electrode to constant weight; Two 2.5cm * 2.5cm gas diffusion electrode is immersed 25.0ml contain in the ethanolic soln of 15wt% phosphoric acid, flooded 10 minutes, dry to constant weight for 60 ℃, obtain phosphate-doped gas diffusion electrode; One side of two phosphate-doped gas diffusion electrode platiniferous C catalysts is gathered [2 to high temperature proton exchange film is phosphate-doped; 2 '-(to the oxygen diphenylene)-5; 5 '-bisbenzimidazole] the film placement; 150 ℃, 1MPa hot pressing 10 minutes obtain a kind of polybenzimidazole sticker and are used for fuel cell membrane electrode, and wherein polybenzimidazole sticker molecular weight is 9400.
Fig. 1 is a kind of polybenzimidazole sticker of embodiment 1 preparation, is used for the polarization performance curve of hydrogen-oxygen fuel cell with the fuel cell membrane electrode of this polybenzimidazole adhesive preparation.160 ℃ of fuel cell test temperature, hydrogen flow rate 100ml/min, oxygen gas flow rate 150ml/min, under the no humidified condition, maximum power density 366mW/cm
2(976mA/cm
2, 0.375V).
Embodiment 2
The preparation of polybenzimidazole sticker: with 2.5mmol (0.5355g) 3,3 ', 4; 4 '-tetramino biphenyl and 2.65mmol (0.4402g) m-phthalic acid joins 18.0g and contains in the polyphosphoric acid of 70wt% Vanadium Pentoxide in FLAKES; Under nitrogen protection, 150 ℃ of reactions 2 hours, reacted 20 hours down at 220 ℃ afterwards earlier; Drop to 10 ℃ then, precipitating is in water; With alkali neutralization, filter again, be washed till neutrality after, 100 ℃ of vacuum dryings obtain the polybenzimidazole sticker to constant weight, its molecular weight is 5000.
The polybenzimidazole sticker is used for the preparation of fuel cell membrane electrode: the polybenzimidazole sticker of 0.0130g is dissolved in the 1.3g 1-Methyl-2-Pyrrolidone; Add 0.0391g 20wt% platinum C catalyst again; Stirred 24 hours, and ultrasonic 20 minutes, made electrode slurry; Electrode slurry is coated on two 2.5cm * 2.5cm gas diffusion layers, and 190 ℃ of vacuum dryings obtain gas diffusion electrode to constant weight; Two 2.5cm * 2.5cm gas diffusion electrode is immersed 12.5ml contain in the ethanolic soln of 15wt% phosphoric acid, flooded 30 minutes, dry to constant weight for 80 ℃, obtain phosphate-doped gas diffusion electrode; One side of two phosphate-doped gas diffusion electrode platiniferous C catalysts is gathered [2 to phosphate-doped; 2 '-(to the oxygen diphenylene)-5; 5 '-bisbenzimidazole] the film placement; 160 ℃, 2MPa hot pressing 1 minute obtain a kind of polybenzimidazole sticker and are used for fuel cell membrane electrode, and wherein polybenzimidazole sticker molecular weight is 5000.
160 ℃ of fuel cell test temperature, hydrogen flow rate 100ml/min, oxygen gas flow rate 150ml/min, under the no humidified condition, maximum power density 190mW/cm
2(560mA/cm
2, 0.34V).
Embodiment 3
The preparation of polybenzimidazole sticker: with 10.0mmol (2.1420g) 3,3 ', 4; 4 '-tetramino biphenyl and 10.2mmol (1.6945g) m-phthalic acid joins 16.0g and contains in the polyphosphoric acid of 90wt% Vanadium Pentoxide in FLAKES; Under nitrogen protection, 50 ℃ of reactions 5 hours, reacted 25 hours down at 200 ℃ afterwards earlier; Drop to 40 ℃ then, precipitating is in water; With alkali neutralization, filter again, be washed till neutrality after, 100 ℃ of vacuum dryings obtain the polybenzimidazole sticker to constant weight, its molecular weight is 16000.
The polybenzimidazole sticker is used for the preparation of fuel cell membrane electrode: the polybenzimidazole sticker of 0.0078g is dissolved in the 4.7g DMSO 99.8MIN., adds 0.0391g 20wt% platinum C catalyst again, stirred 24 hours, ultrasonic 30 minutes, make electrode slurry; Electrode slurry is coated on two 2.5cm * 2.5cm gas diffusion layers, and 190 ℃ of vacuum dryings obtain gas diffusion electrode to constant weight; Two 2.5cm * 2.5cm gas diffusion electrode is immersed 62.5ml contain in the ethanolic soln of 15wt% phosphoric acid, flooded 2 minutes, dry to constant weight for 70 ℃, obtain phosphate-doped gas diffusion electrode; One side of two phosphate-doped gas diffusion electrode platiniferous C catalysts is gathered [2 to phosphate-doped; 2 '-(to the oxygen diphenylene)-5; 5 '-bisbenzimidazole] the film placement; 100 ℃, 4MPa hot pressing 20 minutes obtain a kind of polybenzimidazole sticker and are used for fuel cell membrane electrode, and wherein polybenzimidazole sticker molecular weight is 16000.
160 ℃ of fuel cell test temperature, hydrogen flow rate 100ml/min, oxygen gas flow rate 150ml/min, under the no humidified condition, maximum power density 352mW/cm
2(950mA/cm
2, 0.37V).
Claims (6)
1. the preparation method of a polybenzimidazole sticker is characterized in that the preparation method is following:
With 3,3 ', 4,4 '-tetramino biphenyl and m-phthalic acid join in the polyphosphoric acid that contains the 70-90wt% Vanadium Pentoxide in FLAKES; 3,3 ', 4, the mol ratio of 4 '-tetramino biphenyl and m-phthalic acid is 1:1.02-1:1.06; 3,3 ', 4, the total mass concentration of 4 '-tetramino biphenyl and m-phthalic acid is 5-20wt%; Under nitrogen protection, in 50-220 ℃ of reaction 5-30 hour, drop to 10-40 ℃ then, precipitating is in water; With alkali neutralization, filter again, be washed till neutrality after, 100 ℃ of vacuum dryings obtain a kind of polybenzimidazole sticker to constant weight, its molecular weight is 5000-16000.
2. application of the polybenzimidazole sticker for preparing of method according to claim 1 is characterized in that application method is following:
1 mass parts polybenzimidazole sticker is dissolved in the 100-2000 mass parts organic solvent, adds the platinum C catalyst of 3-20 mass parts again, stir the ultrasonic electrode slurry of making; Electrode slurry is coated on the gas diffusion layers, and 190 ℃ of vacuum dryings obtain gas diffusion electrode to constant weight; The gas diffusion electrode immersion is contained in the ethanolic soln of 15wt% phosphoric acid; Wherein every square centimeter of required volumes of aqueous ethanol that contains 15wt% phosphoric acid of gas diffusion electrode is 1-5ml; Flooded 2-30 minute, and dried to constant weight for 60-80 ℃, obtain phosphate-doped gas diffusion electrode; One side of two phosphate-doped gas diffusion electrode platiniferous C catalysts is placed to high temperature proton exchange film; 100-160 ℃, 1-4MPa hot pressing 1-20 minute; Obtain a kind of polybenzimidazole sticker and be used for fuel cell membrane electrode, wherein polybenzimidazole sticker molecular weight is 5000-16000.
3. according to the application of the described a kind of polybenzimidazole sticker of claim 2, it is characterized in that organic solvent is DMAC N,N, 1-Methyl-2-Pyrrolidone or DMSO 99.8MIN..
4. according to the application of the described a kind of polybenzimidazole sticker of claim 2, it is characterized in that the platinum C catalyst is the platinum C catalyst that contains 10-60wt% platinum.
5. according to the application of the described a kind of polybenzimidazole sticker of claim 2, it is characterized in that gas diffusion layers is carbon paper, carbon cloth or the carbon felt of the smooth processing of hydrophobic.
6. according to the application of the described a kind of polybenzimidazole sticker of claim 2; It is characterized in that high temperature proton exchange film is sulfonation polyimidazole film, sulfonated polyphenyl and imidazoles film, sulfonated polyether benzoglyoxaline film, sulfuric acid doping polybenzimidazole membrane or phosphate-doped polybenzimidazole membrane, the molecular weight of high temperature proton exchange film is 10000-200000.
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| CN102585224A (en) * | 2012-03-16 | 2012-07-18 | 华中师范大学 | Polybenzimidazole high temperature resistant material and preparation method thereof |
| CN105742649B (en) * | 2014-12-11 | 2018-02-06 | 中国科学院大连化学物理研究所 | A kind of high temperature proton exchange film fuel cell membrane electrode and preparation method thereof |
| CN113054192A (en) * | 2021-03-11 | 2021-06-29 | 珠海冠宇电池股份有限公司 | Binder and lithium ion battery using same |
| CN114437351B (en) * | 2022-01-11 | 2023-07-28 | 深圳大学 | Preparation method and application of high-temperature fuel cell adhesive |
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| US7038007B2 (en) * | 2004-07-02 | 2006-05-02 | Pbi Performance Products, Inc. | Process for a continuous polymerization for the production of high molecular weight polybenzimidazole |
| CN101220162A (en) * | 2007-12-06 | 2008-07-16 | 上海交通大学 | Production method for 2 or multi-halohydrocarbon crosslinked polybenzimidazole crosslinked membrane |
| CN101456964A (en) * | 2008-12-23 | 2009-06-17 | 东华大学 | Method for preparing aromatic polybenzimidazole resin film |
| CN101814611A (en) * | 2010-05-24 | 2010-08-25 | 上海交通大学 | Method for preparing phosphate-doped polybenzimidazole membrane electrode for fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7038007B2 (en) * | 2004-07-02 | 2006-05-02 | Pbi Performance Products, Inc. | Process for a continuous polymerization for the production of high molecular weight polybenzimidazole |
| CN101220162A (en) * | 2007-12-06 | 2008-07-16 | 上海交通大学 | Production method for 2 or multi-halohydrocarbon crosslinked polybenzimidazole crosslinked membrane |
| CN101456964A (en) * | 2008-12-23 | 2009-06-17 | 东华大学 | Method for preparing aromatic polybenzimidazole resin film |
| CN101814611A (en) * | 2010-05-24 | 2010-08-25 | 上海交通大学 | Method for preparing phosphate-doped polybenzimidazole membrane electrode for fuel cell |
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