CN101140990A - Application of electric pole gaseous diffusion layer in fuel batter with proton exchange film - Google Patents
Application of electric pole gaseous diffusion layer in fuel batter with proton exchange film Download PDFInfo
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Abstract
The invention relates to an application of electrode gas diffusion layer in proton exchanging membrane fuel cell, taking metal net carrying carbon powder and lyophobic organic compound as the electrode gas diffusion layer. The preparation method is to make one surface or both surfaces of the metal net flat by carbon powder and lyophobic organic compound, and processing the metal net with the high temperature of 290 to 380 degrees centigrade under the protection of inert gases, by which the electrode gas diffusion layer is obtained and used in proton exchanging membrane fuel cell to instead of carbon paper or carbon cloth under the disposal of dewatering and flatting currently in current use. The electrode diffusion layer is characterized in burliness and fastness, being able to make into different shapes like tubular electrode, convinient electrode flowcombine and easy mass production.
Description
Technical field
The present invention relates to a kind of application of electric pole gaseous diffusion layer, is a kind of preparation of electric pole gaseous diffusion layer and the application in Proton Exchange Membrane Fuel Cells thereof specifically.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) that the chemical energy in fuel and the oxidant is directly changed into electric energy by electrochemical reaction.It is to be electrolyte with the solid polymer membrane with good proton-conducting, the anode that a side of film is made up of Catalytic Layer and gas diffusion layers, the negative electrode that opposite side is made up of Catalytic Layer and gas diffusion layers.Anode, solid polymer electrolytic film and negative electrode three press together and constitute Proton Exchange Membrane Fuel Cells (PEMFC) core component-membrane electrode three-in-one (MEA), the three-in-one both sides of membrane electrode are provided with the graphite cake of gas flow channel or surface modification of metals plate (bipolar plates) back constitutes the Proton Exchange Membrane Fuel Cells monocell, and several are superimposed and constitute pile in the filter press mode to hundreds of monocells.Electrochemical reaction during oxidants such as target supply oxygen or air, takes place in fuel such as antianode hydrogen supply, methyl alcohol or reformation gas on membrane electrode is three-in-one, the chemical energy in fuel and the oxidant is converted into electric energy.
When anode is a fuel with hydrogen or methyl alcohol, when negative electrode is oxidant with oxygen or air, under the electrode catalyst effect, following electrode reaction takes place respectively.
Anode: 2H
2→ 4H
++ 4e
-
Perhaps: CH
3OH+H
2O → CO
2+ 6H
++ 6e
-
Negative electrode: O
2+ 4H
++ 4e
-→ 2H
2O
From following formula as can be known, in the Proton Exchange Membrane Fuel Cells (PEMFC), the necessary condition that electrochemical reaction is carried out is the material that should respond, have again proton and electronics supply, conduct and give and accept.Be that electrochemical reaction is to carry out simultaneously on the three phase boundary of reactant gas, proton conductor, electronic conductor, electrode catalyst particle had both played catalytic action, play the effect of conduction electron (electron channel) again, polyelectrolyte plays proton conducting (proton channel).Pore in the electrode plays the effect of the transmission channels of reactant (hydrogen, oxygen), product (water).Electrode diffusion layer plays support, afflux in electrode and for gas, water provide passage, it depends primarily on resistance and porosity to the influence of battery.When the water proofing property difference of electrode, diffusion layer also influences the steady state operation performance of battery.
Generally speaking the preparation method of fuel cell electrode diffusion layer is as follows:
At first carbon paper or carbon cloth are repeatedly immersed in the aqueous emulsion of hydrophobic organic compound such as polytetrafluoroethylene (PTFE), it is made hydrophobic handle, determine the PTFE amount that immerses with weight method.Carbon paper or the carbon cloth of PTFE will have been soaked again, placing temperature is to heat-treat in 330～340 ℃ of baking ovens, and the surfactant that PTFE contained that is immersed in is wherein removed, and makes PTFE hot melt knot simultaneously, and be dispersed on the fiber of carbon paper, thereby reach good hydrophobic effect.Because carbon paper or the recessed injustice of carbon cloth surface imperfection are influential to the preparation Catalytic Layer, therefore need flatten processing to it.Its technical process is:, as solvent carbon black is mixed with PTFE with water or water and ethanol, use ultrasonic oscillation, mix, mixture is transferred on carbon paper or carbon cloth that hydrophobic is handled, constitute regulating course or microporous layers.
People [Gu-Gon Park such as Gu-Gon Park, Young-Jun Sohn, et al, J.PowerSources, 131 (2004) 182] studied PTFE content to being the influence of the proton exchange membrane fuel cell electrode diffusion layer of substrate with the Toray carbon paper, found that the carbon paper regulating course has very big influence to battery performance and water management.
People such as M.V.Willimas [M.V.Williams, E.Begg, et al, J.Electrochem.Soc., 151 (2004), A1173-A1180] etc. the people studied factors such as electronic conductance, porosity, pore size distribution, waterproof pore volume to being the electrode diffusion layer performance impact of substrate with carbon paper, carbon cloth, find that waterproof pore volume, porosity have nothing to do with the electrode limiting current, the macropore content in the diffusion layer has a strong impact on gas transmission therein.
Patent US6605381 provides a kind of preparation method of proton exchange membrane fuel cell electrode diffusion layer, adopts the multilayer carbon paper to handle through hydrophobic and leveling, makes its porosity and water proofing property present Gradient distribution, helps the water management of battery.
Patent WO0025377 provides a kind of preparation method of proton exchange membrane fuel cell electrode diffusion layer, hydrophilic fibers is added in the electrode diffusion layer of carbon cloth preparation, prevents proton exchange membrane dehydration in the battery operation process, helps the water management of battery.
Above-mentioned electrode all is that carbon paper or carbon cloth hydrophobic with process and that leveling is handled are electrode diffusion layer.Because carbon cloth elasticity is big, stops up the gas flow on the bipolar plates easily, also is not applied in the Proton Exchange Membrane Fuel Cells group at present; Though and carbon paper has been applied in the Proton Exchange Membrane Fuel Cells group, its matter is crisp, fragile, and it is thin not allow to be easy to do, and the production cost height, is not easy to be made into different shape as metal.
Summary of the invention
Is that the fuel cell electrode diffusion layer of substrate is fragile in order to overcome above-mentioned with carbon paper or carbon cloth, be difficult for afflux, shortcomings such as cost height, the objective of the invention is wire netting through leveling, hydrophobic treatment, as the proton exchange membrane fuel cell electrode diffusion layer, improve the intensity of electrode diffusion layer, reduce its cost, and help the electrode miniaturization.
To achieve these goals, the technical solution used in the present invention is:
The application of a kind of electric pole gaseous diffusion layer in Proton Exchange Membrane Fuel Cells supports carbon dust and hydrophobic organic compound with wire netting, as electric pole gaseous diffusion layer.
Described wire netting is a kind of among Pt, Au, Ru, Rh, Ag, Ir, Pd, Ti, the Ta; Can be stretching nets, mesh grid or multihole lamina; The loading of carbon dust is 0.5～10mg/cm
2The weight ratio of carbon dust and hydrophobic organic compound is 10: 1～1: 2.
Described electric pole gaseous diffusion layer can prepare according to the following steps,
1) carbon dust is evenly mixed with hydrophobic organic compound, add in entry or the organic solvent and form slurry; The ratio that water or organic solvent account for slurry is 90～99wt%, and the weight ratio of carbon dust and hydrophobic organic compound is 10: 1～1: 2;
2) this slurry is produced on uniformly the one or both sides of wire netting, drying; The loading of carbon dust is 0.5～10mg/cm
2
3) this is had electrode diffusion layer presoma roasting under inert gas shielding of slurry, obtain electric pole gaseous diffusion layer.
Described carbon dust is that XC-72R, acetylene black, Ketjen are black, one or more the mixture in the Peal blackberry, activated carbon; The loading of carbon dust on wire netting is 1～5mg/cm
2In the described slurry, hydrophobic organic compound can be hydrophobic organic compound such as ptfe emulsion, poly-inclined to one side trifluoro-ethylene emulsion, polyvinylidene fluoride emulsion; Described organic solvent is one or more the mixture in ethanol, isopropyl alcohol, ethylene glycol, n-butanol, the ethyl acetate.
Described wire netting can be anticipated before using, and preprocessing process is: with the washing of 0.1～1M sodium hydroxide solution repeatedly, remove surface organic matter earlier, with the washing of 0.1～1M sulfuric acid solution, remove surface metal ion then, use deionized water wash again;
When if used wire netting is the titanium net, behind deionized water wash, again in the oxalic acid aqueous solution of 3～10wt.% 60～80 ℃ boil half an hour, totally stand-by with deionized water wash more at last;
On the described one or both sides that slurry are produced on uniformly wire netting, the method for employing is spraying, dip coated, blade coating or silk screen printing.
Described baking temperature is 30～100 ℃, and be 0.1～3 hour drying time, and preferred baking temperature is 60～80 ℃, and be 0.5～1 hour drying time; Sintering temperature is 250～380 ℃, and the time is 0.1～1 hour, and preferred sintering temperature is 290～360 ℃, and the time is 0.5～1 hour; Described thickness of diffusion layer can be 50～500 μ m, preferably 150～250 μ m.
On described electric pole gaseous diffusion layer, prepare pole catalyze layer again, form proton exchange membrane fuel cell electrode with conventional method.Pole catalyze layer by carbon carry catalytic activity component, perfluor or partially fluorinated solid macromolecule electrolyte, and hydrophobic organic compound constitute, wherein, perfluor or partially fluorinated solid macromolecule electrolyte content are 5～50wt.%, preferably 10～35wt.%; Hydrophobic organic compound content is 0～50wt.%, preferably 10～35wt.%; It is one or more mixed catalyst component among Pt, Au, Ru, Rh, Ag, Ir, Pd, Co, Fe, Ti, the Mn that described carbon carries the catalytic activity component; The loading of catalytic activity component is 20～80wt.%.
Effect of the present invention:
1. support carbon dust through leveling, hydrophobic treatment with wire netting, replace carbon paper or carbon cloth to make the diffusion layer of electrode, not only overcome the shortcoming that carbon paper is frangible, cost is high, and make electrode by welding feasible that collected current becomes.
2, new electrode diffusion layer can be made different shape: as tubular, be particularly suitable for the electrode miniaturization.
3, new electrode diffusion layer is compared with the carbon paper of present use, and cost is low, produces in enormous quantities easily.
4. the preparation method is simple, and the diffusion layer that obtains is even, effective.
Description of drawings
Fig. 1 is the 5cm of the three-in-one formation of membrane electrode of fuel battery negative pole of the present invention, conventional anode and Nafion 117 film preparations
2The monocell CH of the three-in-one formation of membrane electrode of monocell and comparative example preparation
3The i-V curve chart of OH/ oxygen.Operating condition is: normal pressure is humidification oxygen (200ml/min) not, the methanol aqueous solution of 1.0M, 90 ℃ of battery operational temperatures.
Fig. 2 is the 5cm of the three-in-one formation of membrane electrode of fuel cell electrode of the present invention and Nafion NRE-212 film preparation
2The monocell H of the three-in-one formation of membrane electrode of monocell and comparative example preparation
2The i-V curve chart of/air.Operating condition is: normal pressure hydrogen, air, 60 ℃ of battery operational temperatures, 65 ℃ of humidification temperature.
Fig. 3 is the 5cm of the three-in-one formation of membrane electrode of fuel cell electrode of the present invention and Nafion NRE-212 film preparation
2The monocell H of the three-in-one formation of membrane electrode of monocell and comparative example preparation
2The i-V curve chart of/air.Operating condition is: normal pressure hydrogen, air, 60 ℃ of battery operational temperatures, 65 ℃ of humidification temperature.
Fig. 4 is the 5cm of the three-in-one formation of membrane electrode of fuel cell electrode of the present invention and Nafion NRE-212 film preparation
2Monocell H
2The i-V curve chart of/air.Operating condition is: normal pressure hydrogen, air, 60 ℃ of battery operational temperatures, 65 ℃ of humidification temperature.
Fig. 5 is the 5cm of the three-in-one formation of membrane electrode of fuel cell electrode of the present invention and Nafion NRE-212 film preparation
2Monocell H
2The i-V curve chart of/air.Operating condition is: normal pressure hydrogen, air, 60 ℃ of battery operational temperatures, 65 ℃ of humidification temperature.
Embodiment
Also the invention will be further described in conjunction with the accompanying drawings below by embodiment.
Proton exchange membrane fuel cell electrode diffusion layer provided by the invention forms with carbon dust and hydrophobic organic compound leveling for the surface, one or both sides with wire netting.A kind of in for example (but being not limited in this) Pt, Au, Ru, Rh, Ag, Ir, Pd, Ti, Ta, Ni, the stainless (steel) wire of wire netting; Can be stretching nets or mesh grid.Carbon dust as electronic conductor can be, (but being not limited only to this) Vulcan XC-72 for example, acetylene black, carbon dusts such as black pearl.Hydrophobic organic compound can be, for example (but being not limited only to this) polytetrafluoroethylene etc.
Proton exchange membrane fuel cell electrode diffusion layer provided by the invention and preparation method thereof is characterized in that carbon dust and hydrophobic organic compound are evenly mixed the back with known method, for example methods such as (but being not limited only to this) spraying, dip coated, blade coating or silk screen printing are produced on carbon dust and hydrophobic organic compound on the wire netting.Dry back roasting certain hour under higher temperature is removed the surfactant that PTFE contained that is immersed in wherein, makes PTFE hot melt knot simultaneously, thereby reaches good hydrophobic effect.
Embodiment 1:
Cut 2.5cm * 2cm the titanium stretching nets several pieces, about 50 microns of thickness, porosity is 54%.With the washing of 0.1M diluted sodium hydroxide solution repeatedly, remove surface organic matter earlier, with the washing of 0.1M dilution heat of sulfuric acid repeatedly, remove surface metal ion then, use deionized water wash again.Then in the oxalic acid aqueous solution of 10wt% 80 ℃ boil half an hour, totally stand-by with deionized water wash more at last.
With the XC-72R carbon black of 100mg and a certain amount of hydrophobic organic compound (polytetrafluoroethyl-ne ethene PTFE) emulsion and alcohol solvent weighing by a certain percentage good after, under ultrasonic oscillation, be mixed into uniform slurry, wherein to account for the ratio of slurry be 99wt% to ethanol.The weight ratio of the emulsion of carbon black and PTFE is 1: 1.Then, this slurry is fabricated into the both side surface of Ti net with the method for dip coated, obtains fuel cell electrode diffusion layer presoma, the use amount of carbon dust is controlled at 3.5mg/cm in the diffusion layer
2, 60 ℃ of dryings are 1 hour in air, then at 340 ℃, and nitrogen (N
2) protect following roasting to naturally cool to normal temperature after 30 minutes, then in this electrode diffusion layer surface preparation Catalytic Layer.Thickness of diffusion layer is about 250 μ m.
Take by weighing a certain amount of Pt/C catalyst, add an amount of PTFE emulsion and ethanol in proportion, be coated in after evenly mixing through the surface of gas diffusion layers one side of hydrophobization processing in advance and leveling processing, the use amount of Catalytic Layer Pt is 3.5mg/cm
2, after 350 ℃ of roastings, at electrode catalyst laminar surface spraying Nafion solution, its load amount is 0.8mg/cm under nitrogen protection
2This electrode is as the negative electrode of battery.
Galvanic anode adopts carbon cloth (E-Tek company, type ｀ A ') to handle through the PTFE hydrophobic, and method is seen comparative example, and PTFE content is about 20wt%.Mixture with Ketjen 600 carbon blacks and Nafion solution flattens it then, and wherein the use amount of carbon dust is controlled at 2～3mg/cm
2, the about 10wt% of the content of Nafion.Prepare Catalytic Layer more thereon.Catalytic Layer is made up of PtRu black (Johnson Matthey company, the atomic ratio of Pt and Ru is 1: 1) and Nafion, and wherein Nafion content is about 25wt%, and the load amount of the black catalyst of PtRu is about 4mg/cm
2
Anode, the negative electrode that makes placed the both sides of Nafion 117 films, and it is three-in-one to obtain membrane electrode 140 ℃ of hot pressing.The three-in-one both sides of this membrane electrode are added anode and cathode flow field plate respectively, and collector plate and end plate constitute monocell, the about 5cm of electrode effective area
2Infeed the not oxygen of humidification (200ml/min) of normal pressure to negative electrode, anode feeds the methanol solution of 1.0M, 90 ℃ of battery operational temperatures under normal pressure.Estimate the V-i curve chart of battery, the result as shown in Figure 1.
Comparative example:
At first carbon paper (Toray-060) is repeatedly immersed in the ptfe emulsion (PTFE), it is made hydrophobic handle.To soak carbon paper or the carbon cloth of PTFE again, placing temperature is to heat-treat in 330～340 ℃ of baking ovens, and the surfactant that PTFE contained that is immersed in is wherein removed, and makes PTFE hot melt knot simultaneously, thereby reaches good hydrophobic effect.Then it is flattened processing.Its technical process is:, as solvent the XC-72R carbon black is mixed with PTFE with water or water and ethanol, wherein the content of PTFE is 50wt.%, uses ultrasonic oscillation, mixes, and mixture is transferred on the carbon paper that hydrophobic is handled, to its surface evening.The use amount of carbon dust is controlled at 3mg/cm in the diffusion layer
2The method for making of Catalytic Layer as previously mentioned, the use amount of Pt is 3.5mg/cm in the Catalytic Layer
2Obtain the negative electrode of battery.
The galvanic anode preparation method places the both sides of Nafion 117 films with anode, the negative electrode that makes as previously mentioned, and it is three-in-one to obtain membrane electrode 140 ℃ of hot pressing.Estimate the i-V curve of battery under the aforementioned operation condition, the result as shown in Figure 1.
Embodiment 2:
Cut 2.5cm * 2cm the titanium stretching nets several pieces, about 50 microns of thickness, porosity is 54%.With the washing of 0.5M diluted sodium hydroxide solution repeatedly, remove surface organic matter earlier, with the washing of 0.5M dilution heat of sulfuric acid repeatedly, remove surface metal ion then, use deionized water wash again.Then in the oxalic acid aqueous solution of 3wt% 60 ℃ boiled 30 minutes, totally stand-by with deionized water wash more at last.
With the XC-72R carbon black of 100mg and a certain amount of hydrophobic organic compound (polytetrafluoroethylene PTFE) emulsion and isopropanol solvent weighing by a certain percentage good after, under ultrasonic oscillation, be mixed into uniform slurry, wherein to account for the ratio of slurry be 95wt% to isopropyl alcohol.The weight ratio of the emulsion of carbon black and PTFE is 1: 2.Then, this slurry is fabricated into the both side surface of Ti net with the method for blade coating, obtains fuel cell electrode diffusion layer presoma, the use amount of carbon dust is controlled at 5mg/cm in the diffusion layer
2, 30 ℃ of dryings are 3 hours in air, then at 290 ℃, and nitrogen (N
2) protect following roasting to naturally cool to normal temperature after 60 minutes, then in this electrode diffusion layer surface preparation Catalytic Layer.Thickness of diffusion layer is about 350 μ m.
Take by weighing a certain amount of Pt/C catalyst, add an amount of PTFE emulsion and ethanol in proportion, be coated in after evenly mixing through the surface of gas diffusion layers one side of hydrophobization processing in advance and leveling processing, the use amount of Catalytic Layer Pt is 0.4mg/cm
2, after 350 ℃ of roastings, at electrode catalyst laminar surface spraying Nafion solution, its load amount is 0.8mg/cm under nitrogen protection
2With the anode of band Catalytic Layer and the both sides that negative electrode places Nafion NRE-212 film, it is three-in-one to obtain membrane electrode 140 ℃ of hot pressing.
The three-in-one both sides of this membrane electrode are added anode and cathode flow field plate respectively, and collector plate and end plate constitute monocell, the about 5cm of electrode effective area
2Infeed hydrogen and the air of normal pressure through 65 ℃ of humidifications respectively to anode and cathode, battery operated temperature is 60 ℃, measures the V-i curve of battery, sees shown in Figure 2.
Comparative example:
At first carbon paper (Toray-060) is repeatedly immersed in the ptfe emulsion (PTFE), it is made hydrophobic handle.To soak carbon paper or the carbon cloth of PTFE again, placing temperature is to heat-treat in 330～340 ℃ of baking ovens, and the surfactant that PTFE contained that is immersed in is wherein removed, and makes PTFE hot melt knot simultaneously, thereby reaches good hydrophobic effect.Then it is flattened processing.Its technical process is:, as solvent the XC-72R carbon black is mixed with PTFE with water or water and ethanol, wherein the content of PTFE is 50wt.%, uses ultrasonic oscillation, mixes, and mixture is transferred on the carbon paper that hydrophobic is handled, to its surface evening.The use amount of carbon dust is controlled at 2～3mg/cm in the diffusion layer
2
The method for making of Catalytic Layer as previously mentioned, the use amount of Catalytic Layer Pt is 0.4mg/cm
2Two plate electrodes that make are placed the both sides of Nafion NRE-212 film, and it is three-in-one to obtain membrane electrode 140 ℃ of hot pressing, estimates the V-i curve of battery then subject to the foregoing.See shown in Figure 2.
Embodiment 3:
Cut platinum stretching nets a slice of 2.5cm * 2cm, about 100 microns of thickness, porosity is 60%.With the washing of 1M diluted sodium hydroxide solution repeatedly, remove surface organic matter earlier, with the washing of 1M dilution heat of sulfuric acid repeatedly, remove surface metal ion then, use deionized water wash again, totally stand-by.
With the Peal blackberry of 50mg and a certain amount of hydrophobic organic compound (poly-inclined to one side trifluoro-ethylene) emulsion and the weighing by a certain percentage of n-butanol solvent good after, under ultrasonic oscillation, be mixed into uniform slurry, wherein to account for the ratio of slurry be 90wt% to n-butanol, and carbon black is 10: 1 with the weight ratio of the emulsion of poly-inclined to one side trifluoro-ethylene.Then, this slurry is fabricated into the both side surface that Pt nets with the method that sprays, obtains fuel cell electrode diffusion layer presoma, the use amount of carbon dust is controlled at 10mg/cm in the diffusion layer
2, 100 ℃ of dryings are 0.1 hour in air, then at 380 ℃, and argon gas (N
2) protect following roasting to naturally cool to normal temperature after 0.1 hour, then in this electrode diffusion layer surface preparation Catalytic Layer.The about 500 μ m of thickness of diffusion layer.
Take by weighing a certain amount of Pt/C catalyst, add an amount of poly-inclined to one side trifluoro-ethylene emulsion and ethanol in proportion, be coated in after evenly mixing through the surface of gas diffusion layers one side of hydrophobization processing in advance and leveling processing, the use amount of Catalytic Layer Pt is 0.4mg/cm
2, after 350 ℃ of roastings, at electrode catalyst laminar surface spraying Nafion solution, its load amount is 0.8mg/cm under nitrogen protection
2With the anode of band Catalytic Layer and the both sides that negative electrode places Nafion NRE-212 film, it is three-in-one to obtain membrane electrode 140 ℃ of hot pressing.
The three-in-one both sides of this membrane electrode are added anode and cathode flow field plate respectively, and collector plate and end plate constitute monocell, the about 5cm of electrode effective area
2Infeed hydrogen and the air of normal pressure through 65 ℃ of humidifications respectively to anode and cathode, battery operated temperature is 60 ℃, measures the V-i curve of battery, sees shown in Figure 3.
Comparative example is with embodiment 2, and the result as shown in Figure 3.
Embodiment 4:
Cut two of the golden mesh grids of 2.5cm * 2cm, about 50 microns of thickness.With the washing of 0.2M diluted sodium hydroxide solution repeatedly, remove surface organic matter earlier, with the washing of 0.6M dilution heat of sulfuric acid repeatedly, remove surface metal ion then, use deionized water wash again, totally stand-by.
With the acetylene black of 20mg and a certain amount of hydrophobic organic compound (polyvinylidene fluoride) emulsion and deionized water weighing by a certain percentage good after, under ultrasonic oscillation, be mixed into uniform slurry, wherein to account for the ratio of slurry be 92wt% to deionized water, and the weight ratio of the emulsion of carbon black and polyvinylidene fluoride is 10: 5.Then, this slurry is fabricated into the both side surface of Au net with the method for blade coating, obtains fuel cell electrode diffusion layer presoma, the use amount of carbon dust is controlled at 1mg/cm in the diffusion layer
2, 80 ℃ of dryings are 1 hour in air, then at 360 ℃, and argon gas (N
2) protect following roasting to naturally cool to normal temperature after 20 minutes, then in this electrode diffusion layer surface preparation Catalytic Layer.The about 80 μ m of thickness of diffusion layer.
The Catalytic Layer method for making is with embodiment 3, and the use amount of Catalytic Layer Pt is 0.4mg/cm
2Two plate electrodes that make are placed the both sides of Nafion NRE-212 film as anode and negative electrode, and it is three-in-one to obtain membrane electrode 140 ℃ of hot pressing.
The three-in-one both sides of this membrane electrode are added anode and cathode flow field plate respectively, and collector plate and end plate constitute monocell, the about 5cm of electrode effective area
2Infeed hydrogen and the air of normal pressure through 65 ℃ of humidifications respectively to anode and cathode, battery operated temperature is 60 ℃, measures the V-i curve of battery, sees shown in Figure 4.
Embodiment 5:
Cut 2.5cm * 2cm the titanium stretching nets several pieces, about 100 microns of thickness.With the washing of 0.4M diluted sodium hydroxide solution repeatedly, remove surface organic matter earlier, with the washing of 0.8M dilution heat of sulfuric acid repeatedly, remove surface metal ion then, use deionized water wash again.Then in the oxalic acid aqueous solution of 5wt% 70 ℃ boiled 30 minutes, totally stand-by with deionized water wash more at last.
With the Ketjen of 100mg black with a certain amount of hydrophobic organic compound (polyvinylidene fluoride) emulsion and the weighing by a certain percentage of butanediol solvent good after, under ultrasonic oscillation, be mixed into uniform slurry, wherein to account for the ratio of slurry be 96wt% to butanediol, and the weight ratio of the emulsion of carbon black and polyvinylidene fluoride is 10: 6.Then, this slurry is fabricated into the both side surface of Ti net with the method for blade coating, obtains fuel cell electrode diffusion layer presoma, the use amount of carbon dust is controlled at 3mg/cm in the diffusion layer
2, 70 ℃ of dryings are 2 hours in air, then at 250 ℃, and argon gas (N
2) protect following roasting to naturally cool to normal temperature after 1 hour, then in this electrode diffusion layer surface preparation Catalytic Layer.Thickness of diffusion layer is 300 μ m.
The Catalytic Layer method for making is with embodiment 3, and the use amount of Catalytic Layer Pt is 0.4mg/cm
2Two plate electrodes that make are placed the both sides of Nafion NRE-212 film as anode and negative electrode, and it is three-in-one to obtain membrane electrode 140 ℃ of hot pressing.
The three-in-one both sides of this membrane electrode are added anode and cathode flow field plate respectively, and collector plate and end plate constitute monocell, the about 5cm of electrode effective area
2Infeed hydrogen and the air of normal pressure through 65 ℃ of humidifications respectively to anode and cathode, battery operated temperature is 60 ℃, measures the V-i curve of battery, sees shown in Figure 5.
The foregoing description is a case only, the invention is not restricted to this example.
Claims (10)
1. the application of electric pole gaseous diffusion layer in Proton Exchange Membrane Fuel Cells is characterized in that: support carbon dust and hydrophobic organic compound with wire netting, as electric pole gaseous diffusion layer.
2. application according to claim 1 is characterized in that: described wire netting is a kind of in Pt, Au, Ru, Rh, Ag, Ir, Pd, Ti, the Ta net; Can be stretching nets, mesh grid or multihole lamina.
3. application according to claim 1 is characterized in that: the loading of described carbon dust is 0.5～10mg/cm
2The weight ratio of carbon dust and hydrophobic organic compound is 10: 1～1: 2.
4. application according to claim 1 is characterized in that: described electric pole gaseous diffusion layer can prepare according to the following steps,
1) carbon dust is evenly mixed with hydrophobic organic compound, add in entry or the organic solvent and form slurry; The ratio that organic solvent accounts for slurry is 90～99wt%, and the weight ratio of carbon dust and hydrophobic organic compound is 10: 1～1: 2:
2) this slurry is produced on uniformly the one or both sides of wire netting, drying; The loading of carbon dust is 0.5～10mg/cm
2
3) this is had electrode diffusion layer presoma roasting under inert gas shielding of slurry, obtain electric pole gaseous diffusion layer.
5. application according to claim 4 is characterized in that: described carbon dust is that XC-72R, acetylene black, Ketjen are black, one or more the mixture in the Peal blackberry, activated carbon; The loading of carbon dust on wire netting is 1～5mg/cm
2
6. application according to claim 4 is characterized in that: in the described slurry, hydrophobic organic compound can be hydrophobic organic compound ptfe emulsion, poly-inclined to one side trifluoro-ethylene emulsion or polyvinylidene fluoride emulsion; Described organic solvent is one or more the mixture in ethanol, isopropyl alcohol, ethylene glycol, the n-butanol.
7. application according to claim 4, it is characterized in that: described wire netting can be anticipated before using, preprocessing process is: earlier with the washing of 0.1～1M sodium hydroxide solution repeatedly, remove surface organic matter, wash with 0.1～1M sulfuric acid solution then, remove surface metal ion, use deionized water wash again; When if used wire netting is the titanium net, behind deionized water wash, again in the oxalic acid aqueous solution of 3～10wt.% 60～80 ℃ boil half an hour, totally stand-by with deionized water wash more at last;
On the described one or both sides that slurry are produced on uniformly wire netting, the method for employing is spraying, dip coated, blade coating or silk screen printing.
8. application according to claim 4 is characterized in that: described baking temperature is 30～100 ℃, and be 0.1～3 hour drying time; Sintering temperature is 250～380 ℃, and the time is 0.1～1 hour.
9. application according to claim 8 is characterized in that: described baking temperature is 60～80 ℃, and be 0.5～1 hour drying time; Sintering temperature is 290～360 ℃, and the time is 0.5～1 hour.
10. the proton exchange membrane fuel cell electrode that preparation method according to claim 1 makes, it is characterized in that: described thickness of diffusion layer is 50～500 μ m.
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| CNA2006100476846A CN101140990A (en) | 2006-09-08 | 2006-09-08 | Application of electric pole gaseous diffusion layer in fuel batter with proton exchange film |
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| CN102306807A (en) * | 2011-08-17 | 2012-01-04 | 华南理工大学 | Cathode of film-free air microbial fuel cell and manufacturing method thereof |
| CN105428676A (en) * | 2015-08-07 | 2016-03-23 | 杭州电子科技大学 | Proton exchange membrane fuel cell cathode structure for in-situ raman spectroscopy test and testing method |
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| CN112952110B (en) * | 2019-12-11 | 2024-04-09 | 丰田自动车株式会社 | Method for producing gas diffusion layer with microporous layer and method for producing fuel cell |
| CN112993265A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Gas diffusion layer for fuel cell and preparation method thereof |
| CN112838233A (en) * | 2021-01-22 | 2021-05-25 | 中汽创智科技有限公司 | Fuel cell gas diffusion layer, electrode, membrane electrode assembly, single cell and preparation method thereof |
| CN114725398B (en) * | 2022-04-28 | 2023-10-13 | 一汽解放汽车有限公司 | High-pressure-resistant long-life gas diffusion layer, preparation method and fuel cell |
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