CN105261767A - Nano carbon-doped porous fiber single electrode, membrane electrode and preparation method - Google Patents
Nano carbon-doped porous fiber single electrode, membrane electrode and preparation method Download PDFInfo
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Abstract
The invention relates to a nano carbon-doped porous fiber single electrode, a membrane electrode and a preparation method. According to the nano carbon-doped porous fiber single electrode, a semi-ordered porous nano fiber thin film is deposited at one side of a gas diffusion layer material; and a layer of metal nanoparticles with catalytic activity is evenly deposited on the nanofiber surface of the semi-ordered porous nano fiber thin film to form the nano carbon-doped porous fiber single electrode, wherein the semi-ordered porous nano fiber thin film is formed by a co-spun high-molecular polymer nano charged superfine fiber attached with a nano carbon material on the surface, and comprises a co-spun high-molecular polymer doped with the nano carbon material as the component. According to the nano carbon-doped porous fiber single electrode, the semi-ordered porous nano fiber layer is formed by the nano carbon material and a high-molecular polymer solution through electrostatic spinning and cospinning for the first time; a catalyst is sprayed on the porous nano fiber layer; and a mico-pore layer and a catalyst layer are combined into one, so that the properties of a prepared single battery are greatly improved; and the lifetime is greatly prolonged.
Description
Technical field
The present invention relates to semiorder electrostatic spinning nano carbon doping porous fibre single electrode, membrane electrode and preparation method, belong to Proton Exchange Membrane Fuel Cells technical field.The present invention also has the electrode of other battery and has very strong reference.
Technical background
Proton Exchange Membrane Fuel Cells (Protonexchangemembranefuelcell, PEMFC) be a kind of chemical energy in fuel is converted into electric energy by electrochemical reaction mode, except the general characteristic (environmental friendliness, energy conversion efficiency are high, energy density is high) with fuel cell, at room temperature can also start fast, easily discharge without electrolyte loss, water, and life-span length, specific power and specific energy high.Thus in small hydropower station, automobile power and movable power source etc., very wide development space is had.Membrane electrode (Membraneelectrodeassembly, MEA) or be called two electrodes, as the core component of Proton Exchange Membrane Fuel Cells, is the core region of electrochemical reaction.The reasonable structure of MEA directly can not only affect the electric output performance of PEMFC, can also improve the catalyst utilization of PEMFC, reduces fuel cell cost of manufacture, accelerates commercialization process.
Membrane electrode is made up of proton exchange membrane and negative electrode, anode, diffusion layer and Catalytic Layer is comprised respectively in cathode and anode, gas diffusion layers adopts carbon cloth through the process of polytetrafluoroethylene PTFE hydrophobic or carbon paper usually, Main Function is for gas flow provides passage, and play the effect of water management, also take on the task and conducting function that support Catalytic Layer.The Nafion series perfluor type sulfonate film of the proton exchange membrane of current use mainly du pont company, thickness is generally 25 ~ 180 μm.Catalytic Layer is as the pith of membrane electrode, it is the main place of cell reaction, comprise negative electrode and anode catalyst layer, be made up of eelctro-catalyst and binding agent, binding agent generally adopts perfluor type sulfonic acid proton conductor, proton exchange resins solution etc., and normally nano level Pt or the Pt alloying pellet of eelctro-catalyst is dispersed in the black carbon surface of high-specific surface area.Because Precious Metals Resources is rare, cost is high, expensive, so membrane electrode is studied to concentrate on greatly reduce noble metal catalyst consumption.Except material own in membrane electrode, its structure and preparation technology are the key technologies of PEMFC research, decide its chemical property and practicality.
Membrane electrode experienced by two stages: catalyst mainly adopts the methods such as silk screen printing, coating, spraying and curtain coating to be prepared into gas diffusion layers on the surface by first generation membrane electrode, sintering, dipping Nafion solution, electrode is formed after drying, then between two-layer electrode, proton exchange membrane is put into hot-forming, this preparation technology is simple, but Catalytic Layer and proton exchange membrane are in conjunction with poor, and catalyst granules likely enters into gas diffusion layers hole, reduce catalyst utilization in membrane electrode; Second generation membrane electrode adopts transfer printing or direct spraying method to be directly prepared in proton exchange membrane by catalyst pulp, and compared with the first generation, the method is easier, and Catalytic Layer is combined with proton exchange membrane better, not easily peel off, catalyst utilization is higher, and the membrane electrode life-span is longer.The first generation and second generation membrane electrode catalytic layer are all that catalyst and electrolyte solution are mixed with certain proportion and form, the multiphase transmission passage of the materials such as proton, electronics, gas and water is all in disordered state, there is stronger electrochemical polarization and concentration polarization, the heavy-current discharge of restriction membrane electrode.In a word, front two generation membrane electrode integrated performance index can't meet PEMFC technology commercialization requirement.The Development Technology index of clear and definite following membrane electrode in USDOE 2013 " FuelCellTechnicalRoadmap ", wherein the year two thousand twenty membrane electrode target is: power density 1000mW/cm
2, accelerated life 5000h, cost 14 ＄/kW.Therefore, membrane electrode will reach commercialization acceptable degree and must accomplish following 2 points: the catalytic activity (platinum family element PGM consumption is 0.125g/kW) that (1) is high; (2) high current density (reaching 0.44A/mgPGM at 0.9V) under low Pt carrying capacity.A new generation's membrane electrode from the ordering angle of multiphase transmission passage realizing the materials such as proton in three phase boundary, electronics, gas and water, must improve catalyst utilization, improves the combination property of fuel cell further.Such as, Minnesota Mining and Manufacturing Company, using directed organic dyestuff whisker as catalyst carrier, whisker sputters Pt as Catalytic Layer by physical vapour deposition (PVD).This whisker can eliminate the corrosion of carrier under high potential, and Catalytic Layer film is thinner than common carbon carrier, and structure is conducive to mass transfer higher at higher current densities.Wuhan University of Technology wood scholar spring (CN102738478A; CN102738477A; CN102760899A; CN102723509A; CN102723500A) adopt masterplate method to synthesize ordering membrane electrode, effectively reduce Catalytic Layer thickness and decrease the consumption of Pt, but manufacture method needs into a bit optimizing, to realize scale preparation.Recently, the people (CN103413950A such as wooden scholar's spring; CN103413947A) report again by the method for electrostatic spinning respectively by polymer nanofiber deposition on the gas diffusion further, the metal nanoparticle with catalytic activity is deposited on polymer nanofiber surface with magnetron sputtering or vacuum deposition method or directly catalyst pulp is sprayed on nano-fiber film side again and form porous single electrode, then be prepared into membrane electrode.But the nano-fiber film conductivity prepared by this method need to improve.
Electrostatic spinning technique is at kilovolt high-magnitude DC electrostatic after the match, the solution of polymer or inorganic matter or solution are ejected from capillary, owing to being subject to electrostatic interaction, the surface tension that the solution gushed out or solution overcome self forms electrified jet, electrified jet moves in the electric field, and form fluid fiber with post-injection solution out or solution, on dash receiver, form fiber membrane after cooling or solvent evaporates.Pt/C catalyst and Nafion mix and utilize electrostatic spinning technique to prepare loose structure cathode catalysis layer by vanderburg university.
Conductive carbon black, nano graphite carbon are the material with carbon elements with low resistance or high resistance performance.Goods conduction or anti-static electrification can be given.Its feature is that particle diameter is little, and specific area is large.If BP2000 is a kind of novel high structure high connductivity carbon black, fine size, specific area is large, and electric conductivity is excellent.The conductivity that nano material effectively can improve nanofiber is prepared with polymer compound.
Carbon nano-tube (CNT), as typical monodimension nanometer material, compared with other conventional carbon materials, has the character of many uniquenesses, such as good conductivity, energy density distribution is high, specific area is large, mechanical property is strong, have hydrogen storage property etc.Therefore, in recent years, CNT receives increasing concern as electrode material.Add heat transfer, conduction and mechanical property etc. that a small amount of carbon nano-tube can improve polymeric material in the polymer, because carbon nano-tube is very easily assembled, affect its dispersion in polymeric matrix and arrangement.Therefore, the key of preparation carbon nano-tube, composite nano-polymers material is to adopt effective method to make carbon nano-tube dispersed and ordered arrangement in polymeric matrix, thus improves the interface binding power between carbon nano-tube and polymeric matrix.Graphene as at present the thinnest in the world be also the hardest nano material, as simple substance, the speed that it at room temperature transmits electronics is all faster than known conductor, is therefore expected to for thinner, conduction speed electronic component of new generation or the electric crystal faster of development.Due to the flaky texture of Graphene, combination that can be good with polymeric matrix; The carboxyl at graphene oxide edge also can be connected with organic component preferably with hydroxy functional group, also can improve the mechanical property of composite material simultaneously.
Summary of the invention
The object of this invention is to provide porous fibre list electricity level, membrane electrode and the preparation method of the doping of a kind of nano-sized carbon.This membrane electrode instead of existing microporous layers by nano-carbon material doping porous fiber film, not only there is same hydrophobic effect, and the structure of the semiorder formed after mixing nano-carbon material makes catalyst can disperse more even, limit the reunion of platinum grain, improve fuel battery service life; Meanwhile, be conducive to expansion and the mass transfer of three phase boundary, this layer of semiorder porous membrane not only has the pliability of polymeric material, and owing to adding nano-carbon material, the conductivity of film is had very large lifting.In addition, the surface roughness affect of this semiorder structure to membrane electrode is less, and improves the multiphase transmission ability of the materials such as proton, electronics, gas and water to a certain extent, and then improves the utilance of catalyst.
To achieve the above object of the invention, technical scheme of the present invention is:
A kind of porous fibre single electrode adopting nano-sized carbon to adulterate is provided, comprise gas diffusion layers and metal nano particle catalysis layer, it is characterized in that: gas diffusion layer material side deposits semiorder porous nano-fibre film, the nanofiber surface uniform deposition of semiorder porous nano-fibre film has the metal nano particle catalysis layer with catalytic activity, be formed by the porous fibre single electrode of nano-sized carbon doping, wherein: described semiorder porous nano-fibre film is made up of the cospinning high molecular polymer nanometer band superfine fibre of surface attachment nano-carbon material, composition is the cospinning high molecular polymer mixing nano-carbon material.
By such scheme, in described semiorder porous nano-fibre film, the mass ratio of nano-carbon material and cospinning high molecular polymer nanometer band superfine fibre is 1:2-9.
By such scheme, described semiorder porous nano-fibre film has the cospinning macromolecule polymer solution system (namely nano-carbon material is dispersed in the system formed in high molecular polymer) of nano-carbon material under high voltage electric field, to form the cospinning high molecular polymer nanometer band superfine fibre of surface attachment nano-carbon material by the method for electrostatic spinning by dispersed, and deposition forms on the gas diffusion.
By such scheme, described gas diffusion layer material is the carbon paper through polytetrafluoroethylene hydrophobic treatment.
By such scheme, described hydrophobic treatment step: immersed by carbon paper in polytetrafluoroethylsolution solution, continue 5 ~ 15 minutes, then be placed in roasting 20-30min in 330 ~ 350 DEG C of baking ovens, wherein in carbon paper, the solid content of polytetrafluoroethylene water-repelling agent is 15 ~ 25%.
By such scheme, described nano-carbon material is the carbon black material (as BP2000, XC72 etc.) of high-specific surface area, carbon nano-tube, as Single Walled Carbon Nanotube (SWCNTs) and multi-walled carbon nano-tubes (MWCNTs), Graphene (graphene), graphene oxide (GO), redox graphene (RGO).
By such scheme, described cospinning high molecular polymer is: Kynoar/polyacrylonitrile, Kynoar/polyvinylpyrrolidone, polyacrylonitrile/polystyrene, polyacrylonitrile/polyvinyl acetate, polyacrylonitrile/polyaniline, Nafion/ polystyrene, Nafion/ polyacrylonitrile.
By such scheme, the charged superfine fibre diameter of described cospinning high molecular polymer, for being less than or equal to 500nm, is less than or equal to 300nm usually.
By such scheme, the thickness of described semiorder porous nano-fibre film (nano-sized carbon doping porous polymer nano-fiber film) is less than or equal to 20 μm, is usually less than or equal to 10 μm.
The unipolar preparation method of porous nano-fibre of described nano-sized carbon doping, comprises the following steps:
(1) nano-carbon material is added containing being conducive to the high molecular polymer of nano-carbon material dissolving as in the solution of polyacrylonitrile, polyvinyl acetate, polyaniline, polystyrene, Nafion, then other high molecular polymerization powder is added as required, dispersed with stirring, obtains the dispersed cospinning macromolecule polymer solution having nano-carbon material;
(2) on the reception cylinder of electrostatic spinning apparatus, gas diffusion layer material is fixed, cylinder is connected with high voltage source negative pole, the dispersed cospinning macromolecule polymer solution having a nano-carbon material prepared in step () is loaded in syringe, be fixed on micro-injection pump, syringe needle is connected with the positive pole of high voltage source, set the fltting speed of syringe pump, start syringe pump, when syringe needle has drop out, open high voltage source, voltage is adjusted to operating voltage electrospinning and obtains nano-sized carbon doping porous polymer nano fibrous membrane;
(3) gas diffusion layers depositing nano-sized carbon doping porous fiber film is put into vacuum drying chamber, be incubated 4 ~ 8h at 60 ~ 80 DEG C, make solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film;
(4) metal nanoparticle with catalytic activity is made pulp spraying and be coated in the gas diffusion layer material side depositing porous polymer fiber membrane, obtain porous single electrode.
By such scheme, the total weight of described high molecular polymerization powder and the mass ratio of nano-carbon material are 2-9:1.By such scheme, in electrostatic spinning, operating voltage is 5 ~ 20kV, and the electrospinning time is 3 ~ 10min.
By such scheme, the constituent of described slurry is metallic catalyst in mass ratio: perfluorinated sulfonic resin: solvent=2 ~ 4:1:5 ~ 30, wherein solvent is isopropyl alcohol, ethylene glycol or ethanol.
By such scheme, when described nano-carbon material is graphene oxide (GO), can in reducing atmosphere, carry out the gas diffusion layer material depositing nano-sized carbon doping porous fiber film reduce that graphene oxide (GO) is reduced to redox graphene (GO) after step (three) complete.
The membrane electrode of the porous fibre single electrode composition providing a kind of nano-sized carbon to adulterate, it is characterized in that: the porous fibre single electrode of the nano-sized carbon doping comprising proton exchange membrane and be fitted in proton exchange membrane both sides forms, and the side and the proton exchange membrane that deposit the metal nanoparticle with catalytic activity in nano-sized carbon doped porous nano fiber single electrode are fitted.
The preparation method of the porous nanofiber membrane electrode of nano-sized carbon doping, comprise the following steps: in the middle of porous fibre single electrode proton exchange membrane being placed on two above-mentioned nano-sized carbon doping, and make to deposit in nano-sized carbon doped porous nano fiber single electrode the side of the metal nanoparticle with catalytic activity and proton exchange membrane is fitted, then membrane electrode is obtained through hot pressing, the pressure of hot pressing is 1 ~ 4MPa, temperature is 90 ~ 160 DEG C, and the time is 20 ~ 120s.
By such scheme, proton exchange membrane material of the present invention comprises the proton exchange resins of the perfluorinated sulfonic resin (Nafion that DuPont produces comprises the Nafion of various length chain) with sulfonic acid group, partially fluorinated proton exchange resins BAM3G and nonfluorinated.
The present invention is by dispersed have the macromolecule polymer solution of nano-carbon material to do presoma cospinning solution not only the to have macromolecular material mechanical property that quality is light, density is little and excellent by the semiorder porous nanofiber membrane that electrostatic spinning technique is prepared into.And nano-carbon material add the conductivity too increasing porous fiber film, except this, in electrostatic spinning process, the high-speed stretch effect of electric field to jet can make nano-carbon material arrange vertically in polymeric matrix, thus gives polymer fiber many excellent properties.Relative to traditional gas diffusion layer material, spray metal nano-particle catalyst on the porous fiber layer of this high-specific surface area, catalytic active area can be increased, improve noble metal utilisation, and relative to traditional micro cavity layer structures, this porous nano-fibre film thickness is thinner, not only has the hydrophobic effect of conventional microporous layer, and this semiorder porous three-dimensional stereochemical structure is more conducive to three phase boundary reaction and mass transfer effect.Membrane electrode of fuel batter with proton exchange film noble metal catalyst consumption of the present invention is few, make efficiency higher than conventional film electrode, and this porous nanofiber membrane thickness is thinner, reduce membrane electrode thickness, by the nanofiber of Polymer materialspreparation, also there is better corrosion resistance, be thus conducive to improving the membrane electrode life-span.
Active metal catalyst of the present invention for supporting precious metal simple substance or precious metal alloys catalyst, described precious metal simple substance be in Pt, Ru, Pd, Rh, Ir, Os any one, described precious metal alloys are M
xn
y, or M
an
bo
c, wherein M, N, O are respectively the arbitrary metallic element in Pt, Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga, Mo, and different, x+y=100 or a+b+c=100.Catalyst loading is 0.05 ~ 0.2mg/cm
2.
The mea with nano-sized carbon doping porous fibrous structure of preparation is dressed up monocell, and it is as follows to carry out electric performance test process:
Monocell assembling and test: be assembled into Proton Exchange Membrane Fuel Cells monocell by having the membrane electrode of nano-sized carbon doped porous nano fibre structure, collector plate, end plate and encapsulant, monocell operating condition is: H
2/ air, air back pressure is 0 ~ 0.1MPa; Cathode and anode humidification degree is 0 ~ 100%; Monocell working temperature is 60 ~ 90 DEG C, and humidification temperature is 80 DEG C.
Compared with background technology, the present invention has the following advantages:
1) first nano-carbon material and macromolecule polymer solution are prepared into nanofibres deposit on gas diffusion layers surface by electrostatic spinning cospinning, form semiorder porous nano-fibre layer, not only increase the conductivity of high molecular polymer, also be conducive to the conduction of the transmission of water and reacting gas and electronics, proton, monocell performance and life-span had and significantly promotes.
2) catalyst is sprayed on this layer of porous nano-fibre layer, microporous layers and Catalytic Layer are united two into one, greatly reduce membrane electrode thickness, not only increase the ordering degree of membrane electrode, also extend three-phase reaction interface and improve mass transfer effect.
3) the carbon dope nano fibrous membrane prepared has very high porosity and specific area, improves utilance and the mass-transfer efficiency of catalyst.
4) carbon dope nano fibrous membrane is by adding different macromolecular material, because of macromolecular material be have that quality is light, density is little and good mechanical performance etc. feature, make the mechanical property of nano fibrous membrane and decay resistance have very large lifting.Preferably adopt the mode of cospinning further, the deficiency of single macromolecular material in toughness and durability can also be compensate for, also meet the homodisperse feature of nano-carbon material simultaneously.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of nano-sized carbon doping porous fiber film in embodiment 1;
Fig. 2 is the transmission electron microscope picture of nano-sized carbon doping porous fiber film in embodiment 1;
Fig. 3 is single electrode scanning electron microscope (SEM) photograph in embodiment 1;
Fig. 4 is the scanning electron microscope (SEM) photograph of non-carbon dope porous fiber film in comparing embodiment 2.
Embodiment
Below by embodiment in detail the present invention is described in detail, the nano-sized carbon doping porous fibre membrane electrode described in embodiment is prepared as stated above.
Embodiment 1
Take 0.5g polyacrylonitrile (PAN) powder, 10gN, dinethylformamide (DMF), be mixed in beaker, at 60 DEG C, 0.5h is stirred with magnetic stirring apparatus, be made into the translucent PAN polymer solution mixed, again 0.3g Single Walled Carbon Nanotube (SWCNTs) is put into polymer solution, ultrasonic 0.5h makes SWCNTs be uniformly dispersed in a polymer solution, magnetic stirring apparatus is used to stir at 50 DEG C again, and add 0.5g Kynoar (PVDF) powder in multiple times on a small quantity, finally obtain mixing cospinning polymer solution.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 350 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.Get the cospinning polymer solution of 2ml ~ 3ml with the syringe of 2ml or 5ml, be fixed on micro-injection pump.Syringe needle adopts the long 7# flat mouth syringe needle for 100cm, and be connected with the positive pole of high voltage source, negative pole is connected with dash receiver.Start syringe pump, regulate syringe fltting speed, when syringe needle has a drop, open high voltage source and regulate operating voltage to be 8.5kv, the electrospinning time is 3min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 6h at 60 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.As shown in Figure 1, 2, as can be seen from Figure: nanofiber diameter is about 250nm, the porosity of porous polymer nano-fiber film is about 90% for ESEM and transmission electron microscope picture.Record film thickness with spiral micrometer and be about 2 μm, nano-carbon material is attached to porous polymer nanofiber surface.By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and isopropyl alcohol in mass ratio 3:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.1mg/cm
2, its scanned picture as shown in Figure 3.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 110 DEG C, the time is 80s.Anode platinum carrying capacity is 0.1mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode, anode 100% is humidified, monocell working temperature 70 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.816 | 0.785 | 0.698 |
Embodiment 2
Take 0.6g polyacrylonitrile (PAN) powder, 10gN, dinethylformamide (DMF), be mixed in beaker, at 60 DEG C, 0.5h is stirred with magnetic stirring apparatus, be made into the translucent PAN polymer solution mixed, again 0.3g multi-walled carbon nano-tubes (MWCNTs) is put into polymer solution, ultrasonic 0.5h makes MWCNTs be uniformly dispersed in a polymer solution, magnetic stirring apparatus is used to stir at 50 DEG C again, and add 0.4g Kynoar (PVDF) powder in multiple times on a small quantity, finally obtain mixing cospinning polymer solution.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 340 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.By its electrospinning in hydrophobic carbon paper side, other concrete steps are as embodiment 1.Opening high voltage source regulates operating voltage to be 9.3kv, and the electrospinning time is 5min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 4h at 80 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.Wherein nanofiber diameter is about 220nm, and film thickness is about 4 μm, and the porosity of porous polymer nano-fiber film is about 90%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and ethylene glycol in mass ratio 4:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.1mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 110 DEG C, the time is 80s.Anode platinum carrying capacity is 0.1mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode, anode 100% is humidified, monocell working temperature 70 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.798 | 0.769 | 0.672 |
Embodiment 3
Take 0.8g polyacrylonitrile (PAN) powder, 10gN, dinethylformamide (DMF), be mixed in beaker, at 60 DEG C, 0.5h is stirred with magnetic stirring apparatus, be made into the translucent PAN polymer solution mixed, again 0.2g graphene oxide (GO) is put into polymer solution, ultrasonic 0.5h makes GO be uniformly dispersed in a polymer solution, magnetic stirring apparatus is used to stir at 50 DEG C again, and add 0.3g Kynoar (PVDF) powder in multiple times on a small quantity, finally obtain mixing cospinning polymer solution.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 330 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.Get the cospinning polymer solution of 2ml ~ 3ml with the syringe of 2ml or 5ml, be fixed on micro-injection pump.Syringe needle adopts the long 9# flat mouth syringe needle for 180cm, is connected with the output of high voltage source.Start syringe pump, regulate syringe fltting speed, when syringe needle has a drop, open high voltage source and regulate operating voltage to be 9.6kv, the electrospinning time is 7min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 5h at 70 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.Wherein nanofiber diameter is about 200nm, and film thickness is about 6 μm, and the porosity of porous polymer nano-fiber film is about 90%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and isopropyl alcohol in mass ratio 4:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.1mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 110 DEG C, the time is 80s.Anode platinum carrying capacity is 0.1mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode, anode 100% is humidified, monocell working temperature 65 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.824 | 0.796 | 0.655 |
Embodiment 4
Take 0.8g polyacrylonitrile (PAN) powder, 10gN, dinethylformamide (DMF), be mixed in beaker, at 60 DEG C, 0.5h is stirred with magnetic stirring apparatus, be made into the translucent PAN polymer solution mixed, again 0.2g graphene oxide (GO) is put into polymer solution, ultrasonic 0.5h makes GO be uniformly dispersed in a polymer solution, magnetic stirring apparatus is used to stir at 50 DEG C again, and add 0.3g Kynoar (PVDF) powder in multiple times on a small quantity, finally obtain mixing cospinning polymer solution.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 350 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.By its electrospinning in hydrophobic carbon paper side, other concrete steps are as embodiment 3.Opening high voltage source regulates operating voltage to be 10.5kv, and the electrospinning time is 7min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 5h at 80 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.Again the carbon paper with porous nano-fibre electrospinning film is put into tube furnace, at pure H
2first 300 DEG C are heated to the speed of 5 DEG C/min under atmosphere, and constant temperature 4h, by the graphene oxide reduction in nano fibrous membrane, obtain redox graphene.Wherein nanofiber diameter is about 250nm, and film thickness is about 6 μm, and the porosity of porous polymer nano-fiber film is about 85%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and ethanol in mass ratio 2:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.1mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 100 DEG C, the time is 90s.Anode platinum carrying capacity is 0.1mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0, and negative electrode, anode 100% is humidified, monocell working temperature 70 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.803 | 0.798 | 0.659 |
Embodiment 5
Take 0.5g polyacrylonitrile (PAN) powder, 10gN, dinethylformamide (DMF), be mixed in beaker, at 60 DEG C, 0.5h is stirred with magnetic stirring apparatus, be made into the translucent PAN polymer solution mixed, again 0.1g Graphene is put into polymer solution, ultrasonic 0.5h makes Graphene be uniformly dispersed in a polymer solution, magnetic stirring apparatus is used to stir at 50 DEG C again, and add 0.4g Kynoar (PVDF) powder in multiple times on a small quantity, finally obtain mixing cospinning polymer solution.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 330 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.By its electrospinning in hydrophobic carbon paper side, other concrete steps are as embodiment 3.Opening high voltage source regulates operating voltage to be 7.8kv, and the electrospinning time is 10min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 8h at 60 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.Wherein nanofiber diameter is about 500nm, and film thickness is about 20 μm, and the porosity of porous polymer nano-fiber film is about 80%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and ethylene glycol in mass ratio 4:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.05mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.15mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 140 DEG C, the time is 60s.Anode platinum carrying capacity is 0.05mg/cm
2, negative electrode platinum carrying capacity is 0.15mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0, and negative electrode, anode 100% is humidified, monocell working temperature 90 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.788 | 0.743 | 0.647 |
Embodiment 6
Take 0.6g polyacrylonitrile (PAN) powder, 10gN, dinethylformamide (DMF), be mixed in beaker, at 60 DEG C, 0.5h is stirred with magnetic stirring apparatus, be made into the translucent polymer solution mixed, again acid-treated for 0.5g conductive black BP2000 is put into polymer solution, ultrasonic 0.5h makes BP2000 be uniformly dispersed in a polymer solution, magnetic stirring apparatus is used to stir at 50 DEG C again, and add 0.4g Kynoar (PVDF) powder in multiple times on a small quantity, finally obtain the cospinning polymer solution mixed.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 350 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.Get the cospinning polymer solution of 2ml ~ 3ml with the syringe of 2ml or 5ml, be fixed on micro-injection pump.Syringe needle adopts the long 7# flat mouth syringe needle for 180cm, is connected with the output of high voltage source.Start syringe pump, regulate syringe fltting speed, when syringe needle has a drop, open high voltage source and regulate operating voltage to be 9.8kv, the electrospinning time is 5min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 8h at 70 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.Wherein nanofiber diameter is about 300nm, and film thickness is about 4 μm, and the porosity of porous polymer nano-fiber film is about 85%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and isopropyl alcohol in mass ratio 4:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.05mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 1MPa, temperature 140 DEG C, the time is 100s.Anode platinum carrying capacity is 0.05mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode, anode 100% is humidified, monocell working temperature 70 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.783 | 0.735 | 0.652 |
Embodiment 7
Take 0.5g polyacrylonitrile (PAN) powder, 10gN, dinethylformamide (DMF), be mixed in beaker, at 60 DEG C, 0.5h is stirred with magnetic stirring apparatus, the translucent PAN polymer solution mixed is made into until all dissolve, polymer solution is put into after being dried by 0.2gXC72 again, ultrasonic 0.5h makes XC72 be uniformly dispersed in a polymer solution, magnetic stirring apparatus is used to stir at 50 DEG C again, and add 0.4g polyvinylpyrrolidone (PVP) powder in multiple times on a small quantity, finally obtain mixing cospinning polymer solution.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 340 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.By its electrospinning in hydrophobic carbon paper side, other concrete steps are as embodiment 6.Opening high voltage source regulates operating voltage to be 12kv, and the electrospinning time is 7min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 8h at 80 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.Wherein nanofiber diameter is about 350nm, and film thickness is about 6 μm, and the porosity of porous polymer nano-fiber film is about 90%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and glycerol in mass ratio 2:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.1mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 160 DEG C, the time is 50s.Anode platinum carrying capacity is 0.1mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode 100% is humidified, and anode is humidification not, monocell working temperature 80 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.792 | 0.756 | 0.641 |
Embodiment 8
Take 0.5g polyacrylonitrile (PAN) powder, 10gN, dinethylformamide (DMF), be mixed in beaker, at 60 DEG C, 0.5h is stirred with magnetic stirring apparatus, the translucent PAN polymer solution mixed is made into until all dissolve, polymer solution is put into after being dried by 0.2gSMCNTs again, ultrasonic 0.5h makes XC72 be uniformly dispersed in a polymer solution, magnetic stirring apparatus is used to stir at 50 DEG C again, and add 0.4g polystyrene (PS) powder in multiple times on a small quantity, finally obtain mixing cospinning polymer solution.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 330 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.By its electrospinning in hydrophobic carbon paper side, other concrete steps are as embodiment 1.Opening high voltage source regulates operating voltage to be 12kv, and the electrospinning time is 10min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 7h at 60 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.Wherein nanofiber diameter is about 450nm, and film thickness is about 15 μm, and the porosity of porous polymer nano-fiber film is about 80%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and ethylene glycol in mass ratio 4:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.15mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 110 DEG C, the time is 80s.Anode platinum carrying capacity is 0.15mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode, anode 100% is humidified, monocell working temperature 90 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.801 | 0.724 | 0.635 |
Embodiment 9
Take 0.6g polyvinyl acetate (PVAc) powder, 10g carrene (CH
2cl
2), be mixed in beaker, at 50 DEG C, 0.5h is stirred with magnetic stirring apparatus, the translucent PVAc solution mixed is made into until all dissolve, put into polymer solution after being dried by 0.2gGO, ultrasonic 0.5h makes GO be uniformly dispersed in a polymer solution, then is used magnetic stirring apparatus to stir at 50 DEG C again, and add 0.4g polyacrylonitrile (PAN) powder in multiple times on a small quantity, finally obtain mixing cospinning polymer solution.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 350 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.By its electrospinning in hydrophobic carbon paper side, other concrete steps are as embodiment 3.Opening high voltage source regulates operating voltage to be 10kv, and the electrospinning time is 7min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 6h at 60 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.Wherein nanofiber diameter is about 250nm, and film thickness is about 6 μm, and the porosity of porous polymer nano-fiber film is about 85%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and isopropyl alcohol in mass ratio 4:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.1mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 140 DEG C, the time is 60s.Anode platinum carrying capacity is 0.15mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode, anode 100% is humidified, monocell working temperature 90 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.821 | 0.797 | 0.706 |
Embodiment 10
Take 0.6g polyaniline powder, 10gN, dinethylformamide (DMF), be mixed in beaker, at 50 DEG C, 0.5h is stirred with magnetic stirring apparatus, the translucent polyaniline solutions mixed is made into until all dissolve, polymer solution is put into after being dried by 0.2gGO again, ultrasonic 0.5h makes GO be uniformly dispersed in a polymer solution, magnetic stirring apparatus is used to stir at 50 DEG C again, and add 0.4g polyacrylonitrile (PAN) powder in multiple times on a small quantity, finally obtain mixing cospinning polymer solution.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 340 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.By its electrospinning in hydrophobic carbon paper side, other concrete steps are as embodiment 1.Opening high voltage source regulates operating voltage to be 15kv, and the electrospinning time is 5min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 5h at 70 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.Wherein nanofiber diameter is about 250nm, and film thickness is about 4 μm, and the porosity of porous polymer nano-fiber film is about 85%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and isopropyl alcohol in mass ratio 3:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.15mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
The Nafion211 proton exchange membrane of DuPont is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, fuel cell membrane electrode is obtained through hot pressing, hot pressing pressure is 2MPa, temperature 110 DEG C, the time is 80s. anode platinum carrying capacity is 0.15mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode, anode 100% is humidified, monocell working temperature 70 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.816 | 0.789 | 0.713 |
Embodiment 11
By the Nafion solution of 5% and polystyrene according to Nafion: polystyrene is the mass ratio of 6:4, total weight 12.4g, be made into the electrospun solution mixed, polymer solution is put into after being dried by 0.2g multi-walled carbon nano-tubes (WMCNTs) again, ultrasonic 1h makes WMCNTs be uniformly dispersed in a polymer solution, again it is stirred at normal temperatures with magnetic stirring apparatus, finally obtain mixing cospinning polymer solution.The reception cylinder of electrostatic spinning apparatus fixes the gas diffusion layer material through hydrophobic treatment, the process of hydrophobic treatment is immersed in by carbon paper in polytetrafluoroethylene water-repelling agent, time is 10 minutes, and calcines 30 minutes at 350 DEG C, and wherein water-repelling agent solid content is 15 ~ 25wt%.By its electrospinning in hydrophobic carbon paper side, other concrete steps are as embodiment 1.Opening high voltage source regulates operating voltage to be 20kv, and the electrospinning time is 7min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 6h at 80 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film.Wherein nanofiber diameter is about 150nm, and film thickness is about 5 μm, and the porosity of porous polymer nano-fiber film is about 90%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and glycerol in mass ratio 4:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.15mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 120 DEG C, the time is 90s.Anode platinum carrying capacity is 0.15mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode, anode 100% is humidified, monocell working temperature 90 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.813 | 0.725 | 0.661 |
Comparing embodiment 1
The commercial method for preparing membrane electrode of fuel cell: get the hydrophobic carbon paper (microporous layers mixed by polytetrafluoroethylene and electrical-conductive nanometer carbon black with microporous layers, polytetrafluoroethylene content is 10 ~ 30wt%, 20 ~ 30min aftershaping is calcined) at 330 DEG C, by business carbon supported platinum catalyst (mass content of platinum is 60%), 5%Nafion solution and isopropyl alcohol in mass ratio 3:1:20 are mixed and made into slip, and the catalyst slurry that employing obtains is sprayed on the side with microporous layers, platinum carrying capacity is 0.4mg/cm
2.Use the same method and spray above-mentioned catalyst pulp on the hydrophobic carbon paper of another one with microporous layers, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two microporous layers single electrodes being sprayed with catalyst, and makes the side being coated with catalyst touch proton exchange membrane, and obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 110 DEG C, and the time is 80s.Anode platinum carrying capacity is 0.2mg/cm
2, negative electrode platinum carrying capacity is 0.4mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode, anode 100% is humidified, monocell working temperature 70 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.812 | 0.723 | 0.649 |
Comparing embodiment 2
Take 0.5g polyacrylonitrile (PAN) powder, 10gN, dinethylformamide (DMF), be mixed in beaker, stir until it dissolves completely at 60 DEG C with magnetic stirring apparatus, and add 0.5g Kynoar (PVDF) powder in multiple times on a small quantity, finally obtain mixing cospinning polymer solution.By its electrospinning in hydrophobic carbon paper side, other concrete steps are as embodiment 1.Opening high voltage source regulates operating voltage to be 10kv, and the electrospinning time is 3min, obtains porous polymer nanofiber electrospinning film.The hydrophobic carbon paper being stained with porous polymer nanofiber electrospinning film is placed in vacuum drying chamber, is incubated 6h at 60 DEG C, makes solvent evaporates, obtain the gas diffusion layer material depositing porous fiber film.Wherein nanofiber diameter is about 250nm, and as shown in Figure 4, film thickness is about 3 ~ 5 μm, and the porosity of porous polymer nano-fiber film is about 90%.
By the platinum C catalyst (mass content of platinum is 60%) of business, 5%Nafion solution and isopropyl alcohol in mass ratio 3:1:30 are mixed and made into slip, and adopt the catalyst slurry obtained to be sprayed on porous fiber film side, and platinum carrying capacity is 0.1mg/cm
2.
Use the same method and spray above-mentioned catalyst pulp at another one porous nanofiber membrane, platinum carrying capacity is 0.2mg/cm
2.
By DuPont
proton exchange membrane is placed in the middle of two fibrous porous polymer membrane single electrodes being sprayed with catalyst, and make the porous polymer fiber membrane side being coated with catalyst touch proton exchange membrane, obtain fuel cell membrane electrode through hot pressing, hot pressing pressure is 2MPa, temperature 110 DEG C, the time is 80s.Anode platinum carrying capacity is 0.1mg/cm
2, negative electrode platinum carrying capacity is 0.2mg/cm
2.
The mea of preparation is dressed up monocell.
Monocell operating condition is: H
2/ air, air back pressure is 0.1MPa, and negative electrode, anode 100% is humidified, monocell working temperature 70 DEG C.Test result is as follows:
| Electric current (mA/cm 2) | 200 | 600 | 1000 |
| Voltage (V) | 0.758 | 0.735 | 0.650 |
Claims (14)
1. the porous fibre single electrode adopting nano-sized carbon to adulterate, comprise gas diffusion layers and metal nano particle catalysis layer, it is characterized in that: gas diffusion layer material side deposits semiorder porous nano-fibre film, nanofiber surface uniform deposition one deck of semiorder porous nano-fibre film has the metal nano particle catalysis layer of catalytic activity, be formed by the porous fibre single electrode of nano-sized carbon doping, wherein: described semiorder porous nano-fibre film is made up of the cospinning high molecular polymer nanometer band superfine fibre of surface attachment nano-carbon material, composition is the cospinning high molecular polymer mixing nano-carbon material.
2. the porous fibre single electrode of employing nano-sized carbon doping according to claim 1, is characterized in that: in described semiorder porous nano-fibre film, the mass ratio of nano-carbon material and cospinning high molecular polymer nanometer band superfine fibre is 1:2-9.
3. the porous fibre single electrode of employing nano-sized carbon doping according to claim 1, it is characterized in that: described semiorder porous nano-fibre film has the cospinning macromolecule polymer solution system of nano-carbon material under high voltage electric field, to form the cospinning high molecular polymer nanometer band superfine fibre of surface attachment nano-carbon material by the method for electrostatic spinning by dispersed, and deposition forms on the gas diffusion.
4. the porous fibre single electrode of employing nano-sized carbon doping according to claim 1, is characterized in that: described gas diffusion layer material is the carbon paper through polytetrafluoroethylene hydrophobic treatment.
5. the porous fibre single electrode of employing nano-sized carbon doping according to claim 1, is characterized in that: described nano-carbon material is the carbon black material of high-specific surface area, carbon nano-tube, Graphene, graphene oxide, redox graphene.
6. the porous fibre single electrode of employing nano-sized carbon doping according to claim 1, is characterized in that: described cospinning high molecular polymer is: Kynoar/polyacrylonitrile, Kynoar/polyvinylpyrrolidone, polyacrylonitrile/polystyrene, polyacrylonitrile/polyvinyl acetate, polyacrylonitrile/polyaniline, Nafion/ polystyrene, Nafion/ polyacrylonitrile.
7. the porous fibre single electrode of employing nano-sized carbon doping according to claim 1, is characterized in that: the charged superfine fibre diameter of described cospinning high molecular polymer is for being less than or equal to 500nm.
8. the porous fibre single electrode of employing nano-sized carbon doping according to claim 1, is characterized in that: the thickness of described semiorder porous nano-fibre film is less than or equal to 20 μm.
9. the unipolar preparation method of porous nano-fibre of nano-sized carbon doping according to claim 1, is characterized in that: comprise the following steps:
(1) nano-carbon material is added containing being conducive in the solution of the high molecular polymer that nano-carbon material dissolves, then other high molecular polymerization powder is added as required, dispersed with stirring, obtains the dispersed cospinning macromolecule polymer solution having nano-carbon material;
(2) on the reception cylinder of electrostatic spinning apparatus, gas diffusion layer material is fixed, cylinder is connected with high voltage source negative pole, the dispersed cospinning macromolecule polymer solution having a nano-carbon material of joining in step () is loaded in syringe, be fixed on micro-injection pump, syringe needle is connected with the positive pole of high voltage source, set the fltting speed of syringe pump, start syringe pump, when syringe needle has drop out, open high voltage source, voltage is adjusted to operating voltage electrospinning and obtains nano-sized carbon doping porous polymer nano fibrous membrane;
(3) gas diffusion layers depositing nano-sized carbon doping porous fiber film is put into vacuum drying chamber, be incubated 4 ~ 8h at 60 ~ 80 DEG C, make solvent evaporates, obtain the gas diffusion layer material depositing nano-sized carbon doping porous fiber film;
(4) metal nanoparticle with catalytic activity is made pulp spraying and be coated in the gas diffusion layer material side depositing porous polymer fiber membrane, obtain porous single electrode.
10. the unipolar preparation method of porous fibre of employing nano-sized carbon doping according to claim 9, it is characterized in that: in electrostatic spinning, operating voltage is 5 ~ 20kV, the electrospinning time is 3 ~ 10min.
The unipolar preparation method of porous fibre of 11. employing nano-sized carbon doping according to claim 9, it is characterized in that: the constituent of described slurry is metallic catalyst in mass ratio: perfluorinated sulfonic resin: solvent=2 ~ 4:1:5 ~ 30, wherein solvent is isopropyl alcohol, ethylene glycol or ethanol.
The unipolar preparation method of porous fibre of 12. employing nano-sized carbon doping according to claim 9, it is characterized in that: when described nano-carbon material is graphene oxide, after step (three) completes, in reducing atmosphere, carry out the gas diffusion layer material depositing nano-sized carbon doping porous fiber film reduce that graphene oxide is reduced to redox graphene.
The membrane electrode of the porous fibre single electrode composition of 13. 1 kinds of nano-sized carbon doping according to claim 1, it is characterized in that: the porous fibre single electrode of the nano-sized carbon doping comprising proton exchange membrane and be fitted in proton exchange membrane both sides forms, and the side and the proton exchange membrane that deposit the metal nanoparticle with catalytic activity in nano-sized carbon doped porous nano fiber single electrode are fitted.
The preparation method of the porous nanofiber membrane electrode of 14. nano-sized carbon doping according to claim 13, it is characterized in that: comprise the following steps: in the middle of porous fibre single electrode proton exchange membrane being placed on two above-mentioned nano-sized carbon doping, and make to deposit in nano-sized carbon doped porous nano fiber single electrode the side of the metal nanoparticle with catalytic activity and proton exchange membrane is fitted, then membrane electrode is obtained through hot pressing, the pressure of hot pressing is 1 ~ 4MPa, temperature is 90 ~ 160 DEG C, and the time is 20 ~ 120s.
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| CN201510566788.7A CN105261767A (en) | 2015-09-07 | 2015-09-07 | Nano carbon-doped porous fiber single electrode, membrane electrode and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510566788.7A CN105261767A (en) | 2015-09-07 | 2015-09-07 | Nano carbon-doped porous fiber single electrode, membrane electrode and preparation method |
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| CN103441287A (en) * | 2013-08-09 | 2013-12-11 | 中国科学院上海高等研究院 | Preparation method of membrane electrode of direct methanol fuel cell |
-
2015
- 2015-09-07 CN CN201510566788.7A patent/CN105261767A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441287A (en) * | 2013-08-09 | 2013-12-11 | 中国科学院上海高等研究院 | Preparation method of membrane electrode of direct methanol fuel cell |
| CN103413947A (en) * | 2013-08-27 | 2013-11-27 | 武汉理工大学 | Fuel cell ordered porous nano-fiber single electrode, membrane electrode and preparation method |
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| CN107359355B (en) * | 2017-06-12 | 2019-08-16 | 清华大学 | A kind of ordering nanofiber membrane electrode and preparation method thereof |
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| CN107814433B (en) * | 2017-11-01 | 2020-09-08 | 陕西科技大学 | Polymer membrane modified electrode for heavy metal wastewater electrolysis treatment and preparation method thereof |
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| CN109411768A (en) * | 2018-10-17 | 2019-03-01 | 东莞市中航华讯卫星技术有限公司 | The preparation method of air electrode |
| CN109390591A (en) * | 2018-11-19 | 2019-02-26 | 上海华普汽车有限公司 | A kind of battery electrode and its preparation method and application |
| CN109851828B (en) * | 2018-12-03 | 2021-04-16 | 大连理工大学 | Electro-spinning one-dimensional hollow porous inorganic nanofiber doped modified non-fluorine proton exchange membrane and preparation method thereof |
| CN109851828A (en) * | 2018-12-03 | 2019-06-07 | 大连理工大学 | A kind of non-fluorine proton exchange membrane and preparation method thereof of electrospinning one-dimensional hollow porous, inorganic nanofiber doping vario-property |
| CN111584886B (en) * | 2020-05-21 | 2022-06-21 | 上海电气集团股份有限公司 | Carbon nanofiber, diffusion layer, membrane electrode, fuel cell and preparation method and application thereof |
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| CN112030349A (en) * | 2020-09-08 | 2020-12-04 | 北京康烯科技创新研究有限公司 | Non-layered molybdenum nanosheet/graphene-based fiber membrane and preparation method thereof |
| CN112030349B (en) * | 2020-09-08 | 2022-02-15 | 北京康烯科技创新研究有限公司 | Non-layered molybdenum nanosheet/graphene-based fiber membrane and preparation method thereof |
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| CN112251913A (en) * | 2020-10-27 | 2021-01-22 | 中原工学院 | Nano composite conductive fiber membrane with uniform appearance and preparation method and application thereof |
| CN113106629A (en) * | 2021-04-07 | 2021-07-13 | 中国人民解放军国防科技大学 | Ordered nanofiber proton exchange membrane and preparation method and application thereof |
| CN113279150A (en) * | 2021-05-14 | 2021-08-20 | 天津工业大学 | Preparation method of conductive polytetrafluoroethylene porous membrane |
| CN114062443A (en) * | 2021-11-10 | 2022-02-18 | 北京印刷学院 | Flexible sensor for monitoring humidity of package headspace |
| CN114062443B (en) * | 2021-11-10 | 2023-10-03 | 北京印刷学院 | Flexible sensor for monitoring humidity of package headspace |
| CN114678544A (en) * | 2022-04-01 | 2022-06-28 | 昆明理工大学 | Preparation method of 3D multi-stage pore nitrogen-doped carbon-supported monatomic Fe catalyst |
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