CN101814611A - Method for preparing phosphate-doped polybenzimidazole membrane electrode for fuel cell - Google Patents
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Abstract
The invention discloses a method for preparing a phosphate-doped polybenzimidazole membrane electrode for a fuel cell. On the one hand, 4,4'-oxybis(benzoic acid) and 3,3',4,4'-biphenyltetramine serve as monomers to prepare poly[2,2'-(p-oxy- diphenylene)-5-5'-bisbenzimidazole], the poly[2,2'-(p-oxy-diphenylene)-5-5'-bisbenzimidazole] is cast to form a membrane, and the membrane is doped with phosphate to prepare an electrolyte membrane with good mechanical strength; on the other hand, in the process of preparing a phosphate-doped gas diffusion electrode, poly-[2,2'-(m-phenylene)-5,5'-bisbenzimidazole] is prepared into the gas diffusion electrode in the presence of a platinum/carbon catalyst, the gas diffusion electrode is doped with phosphate, the components are uniformly distributed, strong-volatility acid is not used in the process, and a process of mixing solid materials does not exist. The membrane electrode prepared by the method can be used for hydrogen-oxygen fuel cell power generation under the conditions that the temperature is higher than 100 DEG C and the humidification is not carried out. The open-circuit voltage is 0.845V, and the maximum power density is 191mW/cm<2> (560mA/cm<2>, 0.34V) under the conditions that the temperature of the fuel cell is 150DEG C and the humidification is not carried out. The preparation method has the advantages of controllable conditions in the technological process and good repeatability of the process.
Description
Technical field
The present invention relates to a kind of preparation method of membrane-membrane electrode for fuel cell, particularly a kind of fuel cell is with the preparation method of phosphate-doped polybenzimidazoles membrane electrode.
Background technology
Polymer dielectric film type fuel cell system cleaning, efficient, operating temperature is low, and toggle speed is fast, receives much concern in new century chemical industry technical research exploitation.Traditional polymer dielectric film type fuel cell is a dielectric film with the cation-exchange membrane, and the hydrogen that acts as a fuel is directly supplied with anode, supplies with negative electrode as the oxygen or the air of oxidant.In the anode chamber, dissociating under the effect of the anode catalyst of hydrogen in membrane electrode generates proton and electronics, and proton migrates to negative electrode in cation-exchange membrane.Electronics combines generation water with the oxygen of cathode chamber with through the proton that polymer dielectric film passes on the cathod catalyst in membrane electrode, thereby produces electric energy by external circuit and load.
The electrolyte that uses in traditional polymer dielectric film type fuel cell membrane electrode is the perfluorinated sulfonic acid compounds, as business-like Nafion film.This class electrolyte costs an arm and a leg, and leads for making this electrolyte have the high proton electricity, fully hydration of dielectric film.Dehydration and degraded easily take place in this electrolyte under high temperature or the inadequate condition of humidification, make fuel battery performance significantly descend, thereby the corresponding fuel cell normal pressure maximum operating temperature of setting up is 100 ℃.And the required water of electrolyte supplies with by the reaction gas humidification, and humidifier has increased the volume of fuel cell system, has reduced whole efficiency.
The polybenzimidazoles of complete fragrant structure is a class high performance material, has high heat resistance, excellent mechanical property, fabulous chemical stability, good dielectric property and spinning properties, has obtained using widely in fields such as aerospace, microelectronics.In recent years, the researcher finds that phosphate-doped polybenzimidazole membrane is a kind of polymer dielectric film with excellent anti-oxidation characteristics and thermal stability, still can keep than high proton conductivity and certain mechanical strength to 250 ℃ of high temperature.This class material has potential application prospect in novel low-cost high temperature polymer electrolyte membrane type fuel cell field, therefore is subjected to extensive concern.The composition of the polybenzimidazoles dielectric film of main research is poly-[2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] (structural formula is shown in (a)) at present.This compound is the polymer that phenyl ring and armaticity heterocycle constitute, it is relatively poor that strong interaction makes its dissolubility between strand high degree of rigidity and the molecule, and infusibility, cause processing difficulties, the cast film forming need be added cosolvent such as lithium chloride etc. often, the dielectric film mechanical strength for preparing is poor, is unfavorable for practical application.
Poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] contain ehter bond in (structural formula is shown in (b)) structure and make it be dissolved in numerous aprotic solvent easily, as dimethyl sulfoxide (DMSO), 1-Methyl-2-Pyrrolidone, N, N-dimethylacetylamide and pyrovinic acid, filming performance is good.People such as Modestov use potassium hydroxide to mix poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film is the preparation of electrolyte membrane electrode, investigates it and has been used for power generation performance (the Journal of Power Sources 2009 of direct methyl alcohol alkaline fuel cell, 188,502).Dielectric film in this report uses potassium hydroxide to mix, and absorbs carbon dioxide in air easily and generates saleratus and potash, is unfavorable for that fuel cell is in the medium-term and long-term operation of air.The patent disclosure of CN1801511A a kind of preparation method of sour doping polybenzimidazoles membrane electrode, the inventor is made into electrode slurry with polybenzimidazoles compounds, acid, catalyst mix, the dried electrode slurry forms solid material, adds binding material again after the comminuted solids material and is prepared into membrane electrode.For dissolving polybenzimidazoles compounds has used pyrovinic acid and tetrafluoro acetate, these two kinds of acid have strong volatility in this patent, in the mixing of catalyst, can corrode the activity of such catalysts component; Solid material and binding agent mix among the preparation method of this patent disclosure, and both are not easy to mix, and can reduce the power generation performance of fuel cell.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, with 4,4 '-dicarboxyl diphenyl ether and 3,3 ', 4,4 '-tetramino biphenyl is that monomer prepares poly-[2 of good film-forming property by polycondensation reaction, 2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole], phosphate-doped with carrying out behind its casting film, make dielectric film with good mechanical strength; In the phosphate-doped gas-diffusion electrode of preparation, will gather [2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] and the platinum C catalyst make carry out after the gas-diffusion electrode phosphate-doped, each uniform component distribution is not used strong volatile acid in the process, do not have solid material mixed process.
A kind of fuel cell of the present invention is as follows with the preparation method of phosphate-doped polybenzimidazoles membrane electrode:
(1) preparation of phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film: get equimolar 3,3 ', 4,4 '-tetramino biphenyl and 4,4 '-dicarboxyl diphenyl ether joins in the polyphosphoric acids that contains the 70-90wt% phosphorus pentoxide 3,3 ', 4,4 '-tetramino biphenyl and 4, the total mass concentration of 4 '-dicarboxyl diphenyl ether is 5-20wt%, under nitrogen protection, in 50-220 ℃ of reaction 5-30 hour, cooling then, precipitating with the alkali neutralization, is filtered in water again, after being washed till neutrality, 100 ℃ of vacuum dryings are gathered [2,2 '-(to the oxygen diphenylene)-5 to constant weight, 5 '-bisbenzimidazole], its molecular weight is 4000-200000; To gather [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] be dissolved in the organic solvent, the concentration of poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] is 0.1-0.2g/ml, in 60-150 ℃ of following casting film, gathered [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film; Poly-[2,2 '-(to the oxygen diphenylene)-5, the 5 '-bisbenzimidazole] film of 1 mass parts was immersed in 20 mass parts to the 2000 mass parts 70-90wt% phosphoric acid 1-7 days, 120 ℃ of vacuum dryings are to constant weight, obtain phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film;
(2) preparation of phosphate-doped gas-diffusion electrode: 1 mass parts poly-[2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] is dissolved in 100-600 mass parts N, in the N-dimethylacetylamide, the platinum C catalyst that adds the 3-5 mass parts again stirs 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 solution of 20wt% phosphoric acid, wherein every square centimeter of required volumes of aqueous ethanol that contains 20wt% 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;
(3) preparation of membrane electrode a: 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, 100-160 ℃ hot pressing 1-20 minute, obtain a kind of fuel cell with phosphate-doped polybenzimidazoles membrane electrode.
The organic solvent that the present invention uses is dimethyl sulfoxide (DMSO), 1-Methyl-2-Pyrrolidone or N, N-dimethylacetylamide.
Poly-[2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] molecular weight that the present invention uses is 20000-200000.
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.
Among the preparation method of a kind of fuel cell of the present invention with phosphate-doped polybenzimidazoles membrane electrode, dielectric film adopts phosphate-doped poly-[2 on the one hand, 2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film, poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] be soluble in dimethyl sulfoxide (DMSO), 1-Methyl-2-Pyrrolidone, N, in the N-dimethylacetylamide, solution viscosity is moderate, good film-forming property guarantees that the dielectric film of final preparation has good mechanical strength; On the other hand in the phosphate-doped gas-diffusion electrode of preparation, to gather [2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] and the platinum C catalyst make carry out after the gas-diffusion electrode phosphate-doped, each uniform component distribution, do not use strong volatile acid such as pyrovinic acid, tetrafluoro acetate in the process, no solid material mixed process.The phosphate-doped polybenzimidazoles membrane electrode of the present invention preparation can be used for hydrogen oxygen fuel cell and generate electricity being higher than under 100 ℃ of no humidification conditions.Use this membrane electrode, 150 ℃ of fuel battery temperatures, under the no humidified condition, open circuit voltage is 0.845V, maximum power density 191mW/cm
2(560mA/cm
2, 0.34V).Preparation method's technical process condition of the present invention is controlled, the process good reproducibility.
Description of drawings
Fig. 1 is used for the discharge performance curve of hydrogen oxygen fuel cell with phosphate-doped polybenzimidazoles membrane electrode for a kind of fuel cell of embodiment 1 preparation.
Fig. 2 is used for the discharge performance curve of hydrogen oxygen fuel cell with phosphate-doped polybenzimidazoles membrane electrode for a kind of fuel cell of Comparative Examples 1 preparation.
Embodiment
With the following Examples, the present invention is further described, not delimit the scope of the invention.
Poly-[2,2 '-(metaphenylene)-5, the 5 '-bisbenzimidazole] that use in following examples provides for Kunshan beautiful jade moral plastic cement Co., Ltd, and molecular weight is 80000.The platinum C catalyst is the platinum C catalyst that BASF FUEL CELL company contains 20wt% platinum.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.
Embodiment 1
(1) phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] preparation of film: with 5mmol (1.071g) 3,3 ', 4,4 '-tetramino biphenyl and 5mmol (1.291g) 4,4 '-dicarboxyl diphenyl ether join 20.0g and contain in the polyphosphoric acids of 80% phosphorus pentoxide, under nitrogen protection, earlier 150 ℃ of reactions 2 hours, reacted 28 hours down at 190 ℃ afterwards, cooling 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 20000; To gather [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] 2.0g and be dissolved in the dimethyl sulfoxide (DMSO) of 20.0ml,, be gathered [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film in 80 ℃ of casting films; Poly-[2,2 '-(to the oxygen diphenylene)-5, the 5 '-bisbenzimidazole] film of 2.0g was immersed in the 40.0g 85wt% SPA 2 days, and 120 ℃ of vacuum dryings obtain phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film to constant weight;
(2) preparation of phosphate-doped gas-diffusion electrode: 0.0078g poly-[2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] is dissolved in 4.3gN, in the N-dimethylacetylamide, add 0.0391g 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 solution of 20wt% phosphoric acid, flooded 10 minutes, dry to constant weight for 60 ℃, obtain phosphate-doped gas-diffusion electrode;
(3) preparation of membrane electrode a: 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, 150 ℃ of hot pressing 10 minutes obtains a kind of fuel cell with phosphate-doped polybenzimidazoles membrane electrode.
Fig. 1 is used for the discharge performance curve of hydrogen oxygen fuel cell with phosphate-doped polybenzimidazoles membrane electrode for a kind of fuel cell of embodiment 1 preparation.150 ℃ of fuel cell test temperature, under the no humidified condition, hydrogen flow rate 100ml/min, oxygen gas flow rate 150ml/min, open circuit voltage are 0.845V, maximum power density 191mW/cm
2(560mA/cm
2, 0.34V).
Embodiment 2
(1) phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] preparation of film: with 2.5mmol (0.5355g) 3,3 ', 4,4 '-tetramino biphenyl and 2.5mmol (0.6455g) 4,4 '-dicarboxyl diphenyl ether join 22.0g and contain in the polyphosphoric acids of 70% phosphorus pentoxide, under nitrogen protection, earlier 150 ℃ of reactions 2 hours, reacted 20 hours down at 220 ℃ afterwards, cooling 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 4000; To gather [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] 1.0g and be dissolved in the N of 5.0ml, in the N-dimethylacetylamide,, be gathered [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film in 150 ℃ of casting films; Poly-[2,2 '-(to the oxygen diphenylene)-5, the 5 '-bisbenzimidazole] film of 1.0g was immersed in the 100.0g 90wt% SPA 1 day, and 120 ℃ of vacuum dryings obtain phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film to constant weight;
(2) preparation of phosphate-doped gas-diffusion electrode: 0.0130g poly-[2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] is dissolved in 1.3gN, in the N-dimethylacetylamide, add 0.0391g 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 12.5ml contain in the ethanolic solution of 20wt% phosphoric acid, flooded 30 minutes, dry to constant weight for 80 ℃, obtain phosphate-doped gas-diffusion electrode;
(3) preparation of membrane electrode a: 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 ℃ of hot pressing 1 minute obtains a kind of fuel cell with phosphate-doped polybenzimidazoles membrane electrode.
Embodiment 3
(1) phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] preparation of film: with 10mmol (2.142g) 3,3 ', 4,4 '-tetramino biphenyl and 10mmol (2.582g) 4,4 '-dicarboxyl diphenyl ether join 19.0g and contain in the polyphosphoric acids of 90% phosphorus pentoxide, under nitrogen protection, earlier 50 ℃ of reactions 5 hours, reacted 25 hours down at 200 ℃ afterwards, cooling 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 200000; To gather [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] 4.5g and be dissolved in the 1-Methyl-2-Pyrrolidone of 45.0ml,, be gathered [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film in 60 ℃ of casting films; Poly-[2,2 '-(to the oxygen diphenylene)-5, the 5 '-bisbenzimidazole] film of 4.5g was immersed in the 9000.0g 70wt% SPA 7 days, and 120 ℃ of vacuum dryings obtain phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film to constant weight;
(2) preparation of phosphate-doped gas-diffusion electrode: 0.0109g poly-[2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] is dissolved in 6.5gN, in the N-dimethylacetylamide, add 0.0391g 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 solution of 20wt% phosphoric acid, flooded 2 minutes, dry to constant weight for 70 ℃, obtain phosphate-doped gas-diffusion electrode;
(3) preparation of membrane electrode a: 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 ℃ of hot pressing 20 minutes obtains a kind of fuel cell with phosphate-doped polybenzimidazoles membrane electrode.
Comparative Examples 1
(1) phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] preparation of film: with 5mmol (1.071g) 3,3 ', 4,4 '-tetramino biphenyl and 5mmol (1.291g) 4,4 '-dicarboxyl diphenyl ether join 20.0g and contain in the polyphosphoric acids of 80% phosphorus pentoxide, under nitrogen protection, earlier 150 ℃ of reactions 2 hours, reacted 28 hours down at 190 ℃ afterwards, cooling 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 20000; To gather [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] 2g and be dissolved in the dimethyl sulfoxide (DMSO) of 20.0ml,, be gathered [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film in 80 ℃ of casting films; Poly-[2,2 '-(to the oxygen diphenylene)-5, the 5 '-bisbenzimidazole] film of 2g was immersed in the 40.0g 85wt% SPA 2 days, and 120 ℃ of vacuum dryings obtain phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film to constant weight;
(2) preparation of phosphate-doped gas-diffusion electrode: the E-TEK ELAT LT120EW of the BASF FUEL CELL company carbon cloth type gas-diffusion electrode immersion 25.0ml of two 2.5cm * 2.5cm is contained in the ethanolic solution of 20wt% phosphoric acid, flooded 10 minutes, dry to constant weight for 60 ℃, obtain phosphate-doped gas-diffusion electrode;
(3) preparation of membrane electrode a: 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, 150 ℃ of hot pressing 10 minutes obtains a kind of fuel cell with phosphate-doped polybenzimidazoles membrane electrode.
Fig. 2 is used for the discharge performance curve of hydrogen oxygen fuel cell with phosphate-doped polybenzimidazoles membrane electrode for a kind of fuel cell of Comparative Examples 1 preparation.150 ℃ of fuel cell battery probe temperatures, no humidification, hydrogen flow rate 100ml/min, oxygen gas flow rate 150ml/min, open circuit voltage 0.692V, maximum power density only are 78mW/cm
2(276mA/cm
2, 0.28V).
Claims (5)
1. a fuel cell is characterized in that the preparation method is as follows with the preparation method of phosphate-doped polybenzimidazoles membrane electrode:
(1) preparation of phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film: get equimolar 3,3 ', 4,4 '-tetramino biphenyl and 4,4 '-dicarboxyl diphenyl ether joins in the polyphosphoric acids that contains the 70-90wt% phosphorus pentoxide 3,3 ', 4,4 '-tetramino biphenyl and 4, the total mass concentration of 4 '-dicarboxyl diphenyl ether is 5-20wt%, under nitrogen protection, in 50-220 ℃ of reaction 5-30 hour, cooling then, precipitating with the alkali neutralization, is filtered in water again, after being washed till neutrality, 100 ℃ of vacuum dryings are gathered [2,2 '-(to the oxygen diphenylene)-5 to constant weight, 5 '-bisbenzimidazole], its molecular weight is 4000-200000; To gather [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] be dissolved in the organic solvent, the concentration of poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] is 0.1-0.2g/ml, in 60-150 ℃ of following casting film, gathered [2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film; Poly-[2,2 '-(to the oxygen diphenylene)-5, the 5 '-bisbenzimidazole] film of 1 mass parts was immersed in 20 mass parts to the 2000 mass parts 70-90wt% phosphoric acid 1-7 days, 120 ℃ of vacuum dryings are to constant weight, obtain phosphate-doped poly-[2,2 '-(to the oxygen diphenylene)-5,5 '-bisbenzimidazole] film;
(2) preparation of phosphate-doped gas-diffusion electrode: 1 mass parts poly-[2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] is dissolved in 100-600 mass parts N, in the N-dimethylacetylamide, the platinum C catalyst that adds the 3-5 mass parts again stirs 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 solution of 20wt% phosphoric acid, wherein every square centimeter of required volumes of aqueous ethanol that contains 20wt% 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;
(3) preparation of membrane electrode a: 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, 100-160 ℃ hot pressing 1-20 minute, obtain a kind of fuel cell with phosphate-doped polybenzimidazoles membrane electrode.
2. according to the preparation method of the described a kind of fuel cell of claim 1, it is characterized in that organic solvent is dimethyl sulfoxide (DMSO), 1-Methyl-2-Pyrrolidone or N, the N-dimethylacetylamide with phosphate-doped polybenzimidazoles membrane electrode.
3. according to the preparation method of the described a kind of fuel cell of claim 1 with phosphate-doped polybenzimidazoles membrane electrode, the molecular weight that it is characterized in that gathering [2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole] is 20000-200000.
4. according to the preparation method of the described a kind of fuel cell of claim 1, it is characterized in that the platinum C catalyst is the platinum C catalyst that contains 10-60wt% platinum with phosphate-doped polybenzimidazoles membrane electrode.
5. according to the preparation method of the described a kind of fuel cell of claim 1, it is characterized in that gas diffusion layers is carbon paper, carbon cloth or the carbon felt of the smooth processing of hydrophobic with phosphate-doped polybenzimidazoles membrane electrode.
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| CN114628752A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Membrane electrode and preparation and application thereof |
| CN115064745A (en) * | 2022-06-08 | 2022-09-16 | 南东北 | Preparation method of PBI phosphoric acid membrane electrode |
| US11482721B2 (en) | 2018-09-14 | 2022-10-25 | University Of South Carolina | Low permeability polybenzimidazole (PBI) gel membranes for redox flow batteries |
| US11777124B2 (en) | 2020-03-06 | 2023-10-03 | University Of South Carolina | Proton-conducting PBI membrane processing with enhanced performance and durability |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338038A (en) * | 2008-08-07 | 2009-01-07 | 东北大学 | Method for enhancing fracture tensile strength of PBI/HP3O4 cast by sol-gel method |
-
2010
- 2010-05-24 CN CN2010101810224A patent/CN101814611B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338038A (en) * | 2008-08-07 | 2009-01-07 | 东北大学 | Method for enhancing fracture tensile strength of PBI/HP3O4 cast by sol-gel method |
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of Power Sources》 20081206 A.D. Modestova et al. MEA for alkaline direct ethanol fuel cell with alkali doped PBI membrane and non-platinum electrodes 502-506 1-5 第188卷, 2 * |
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| CN114628752B (en) * | 2020-12-11 | 2023-09-19 | 中国科学院大连化学物理研究所 | Membrane electrode and preparation and application thereof |
| CN115064745A (en) * | 2022-06-08 | 2022-09-16 | 南东北 | Preparation method of PBI phosphoric acid membrane electrode |
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