CN101557001B - Fuel cell film electrode and preparation method thereof - Google Patents
Fuel cell film electrode and preparation method thereof Download PDFInfo
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- CN101557001B CN101557001B CN2008103009746A CN200810300974A CN101557001B CN 101557001 B CN101557001 B CN 101557001B CN 2008103009746 A CN2008103009746 A CN 2008103009746A CN 200810300974 A CN200810300974 A CN 200810300974A CN 101557001 B CN101557001 B CN 101557001B
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Abstract
The invention discloses a fuel cell film electrode and a preparation method thereof. The film electrode comprises a gas diffusion layer and catalysis layers, wherein, the catalysis layer is of multilayer composite structure and is mainly composed of a catalytic active metal, a water repellent and a conductive ion polymer, wherein, the conductive ion polymer has different contents among the catalysis layers; the multilayer composite structure has at least two layers, wherein, the first layer is a partial hydrophobic catalysis layer while the second layer is a hydrophilic catalysis layer. The invention further discloses a preparation method of the fuel cell film electrode, wherein, the diffusion layer is prepared by the dry method, the inventive film electrode structure has better water-gas management ability, more uniform and stabler mass transfer and excellent electron and proton conducting ability, thus increasing the utilization rate of catalysts and enhancing electric output performance of the fuel cell.
Description
Technical field
The present invention relates to a kind of fuel cell, specifically relate to a kind of fuel cell membrane electrode and preparation method thereof.
Background technology
The advantages such as fuel cell has the energy conversion efficiency height, easily starts, and environmental pollution is little are considered to following best " clean energy resource ", and many national government all drop into huge fund it is studied.Especially Proton Exchange Membrane Fuel Cells (PEMFCs), because it can be as power source, distributed power station and the Portable movable power supply of motor vehicle, and being subject in recent years the extensive concern of countries in the world, its key technology has also obtained fast development.
Membrane electrode three-in-one (Membrane electrode assembly) is the core component of Proton Exchange Membrane Fuel Cells, the straight gas diffusion layers of its performance quality, usually the porous material by conduction consists of, and effect is collected current, conduction gas and discharge product---water.Desirable diffusion layer should satisfy three conditions: good drainage, good gas permeability, good conductivity.Carbon paper, carbon cloth are present comparatively widely used diffusion layer materials, and thickness is about 100～300 μ m.Its uniform porous structure and low resistivity have guaranteed excellent gas permeability and electronic conduction ability.Owing to only have more single macropore (such as the macropore of about 90% Kong Douwei aperture in the Toray TGP-H-060 carbon paper greater than 20mm) in carbon paper or the carbon cloth, if therefore directly used as the gas diffusion layers of PEMFC monocell, often can not realize effective mass transfer of water and reaction gas.Therefore need between carbon paper or carbon cloth and Catalytic Layer, add microporous layers (the Micro-porous layer that one deck is made by the mixture of carbon dust and PTFE, MPL), can effectively improve the gentle transmission of water among the PEMFC, thereby reduce battery in the concentration polarization of high current density region, improve battery performance.Common preparation method is that wet method prepares microporous layers, and namely the mixture as solvent of the low mass molecule alcohol such as water or water and ethanol is evenly mixed according to certain ratio ultrasonic wave with carbon dust and PTFE emulsion, and heating makes it become the slurry with certain viscosity.Again slurry is coated on the basalis surface of processing through hydrophobization, and carries out sintering processes at 340～350 ℃.Because the proportion of slip penetrates into greatly the inside of carbon paper or carbon cloth easily, and at first is attached to its fiber compact district, causes the inhomogeneous of microporous layers.And the wet method preparation process is complicated, needs to use a large amount of organic low molecular alcohol.
The preparation of Catalytic Layer mainly contains three kinds at hydrophobic electrode, hydrophilic electrode and superthin layer electrode.Traditional hydrophobic electrode is because Catalytic Layer is thicker, and hydrophober content is larger, and internal resistance is larger; And ionic conductive polymer (Nafion) is to enter on the Catalytic Layer surface by the mode that sprays into or immerse, so it is inner and fully contact with catalyst granules to be difficult to guarantee that it fully penetrates into Catalytic Layer, the H+ conduction resistance is large.Do not have water-repelling agent in the thin layer hydrophilic electrode Catalytic Layer, gas passage is less, and the gas transfer resistance is larger; And with Nafion bonding catalyst, its bond strength can descend gradually in long-term work, thereby reduce the performance of electrode.The superthin layer electrode then is that the method by sputtering sedimentation is prepared into catalyst on the electrode, and condition is relatively harsher, is unsuitable for large-scale production.
Summary of the invention
The purpose of this invention is to provide membrane electrode of a kind of fuel cell and preparation method thereof, with the dry process diffusion layer, and adopt the Catalytic Layer preparation technology of multi-layer compound structure, Effective Raise aqueous vapor managerial ability and the three-phase reaction interface of porous electrode, thereby improve fuel battery performance.
Its concrete technical scheme is as follows: a kind of membrane electrode of fuel cell, comprise gas diffusion layers and Catalytic Layer, and described Catalytic Layer is multi-layer compound structure, mainly is comprised of catalyst, hydrophober and conductive ion polymer; The content of wherein said conductive ion polymer between each Catalytic Layer is different; Described multi-layer compound structure is coated with hydrophilic Catalytic Layer for to be coated with part hydrophobic Catalytic Layer and/or hydrophobic Catalytic Layer at gas diffusion layers on it.Can realize different hydrophilic and hydrophobic between each layer by changing the content of conductive ion polymer between each Catalytic Layer.
In the described two-layer catalyst layer structure, described part hydrophobic Catalytic Layer mainly is comprised of the first catalyst, hydrophober and conductive ion polymer; Described hydrophobic Catalytic Layer is comprised of catalyst and hydrophober; Described hydrophilic Catalytic Layer mainly is comprised of the second catalyst and conductive ion polymer.In described hydrophilic Catalytic Layer, do not use hydrophober, thereby reduced the internal resistance of electrode.
The thickness of described part hydrophobic Catalytic Layer and/or hydrophobic Catalytic Layer is 5～15 μ m, and the thickness of described hydrophilic Catalytic Layer is 1～5 μ m.
Described the first catalyst and the second catalyst can be the same catalyst, it also can be different catalyst, it can be that carbon carries platinum, platinum black or alloy catalyst, and described alloy catalyst can be comprised of two kinds of following metal at least: Pt, Pd, Au, Fe, Co, Rh, Ni, Sn, Ru isoreactivity metal.
Described conductive ion polymer is perfluorinated sulfonic acid resin (Nafion solution), or polyether-ether-ketone (S-PEEK), the polysulfones (S-PS) processed through oversulfonate.
Described hydrophober is polytetrafluoroethylene (PTFE) emulsion, Kynoar (PVDF) emulsion, fluorinated ethylene propylene (FEP) (FEP) emulsion, or polytrifluorochloroethylene (PCTFE) suspension.
A kind of preparation method of fuel cell membrane electrode, its key step is as follows:
1) porous basic unit is immersed fully wetting in 1%～20% the fluoropolymer emulsion after, take out dry; Repeat above-mentioned steps until the content of fluoropolymer reaches 5%～60%, then 200～380 ℃ of heat treatment 10～60min in high temperature oven;
2) taking by weighing mass ratio is 10: conductive carbon powder and the fluoropolymer powder of 0.5-10, the high speed ball milling mixes, obtain composite powder, then composite powder is applied in the porous basic unit, make microporous layers, then the gas diffusion layers that makes is placed 200～380 ℃ of heat treatment 10～60min of high temperature oven thereby make gas diffusion layers;
3) catalyst and low mass molecule alcohol are mixed according to 1: 1～50 mass ratio, behind ultrasonic agitation 1～20min, make ink shape slip, then be that 1～10: 1 mass ratio adds hydrophober in above-mentioned slip according to catalyst/hydrophober, then behind ultrasonic agitation 30～60min, be applied to step 2) on the gas diffusion layers of preparation, then in high temperature oven, behind 150～400 ℃ of lower burning 10～60min, make Catalytic Layer; And/or be after 1: 1～5 mass ratio mixes, to be applied on the above-mentioned Catalytic Layer according to conductive ion polymer/dispersant, then place 60～120 ℃ of drying 1～10h of vacuum drying chamber, make part hydrophobic Catalytic Layer and/or hydrophobic Catalytic Layer;
4) catalyst and low mass molecule alcohol are mixed according to 1: 1～50 mass ratio, make slip, be that 1～5: 1 mass ratio adds the conductive ion polymer in above-mentioned slip according to catalyst/conductive ion polymer then, behind ultrasonic agitation 30～60min, make mixed slurry, then above-mentioned mixed slurry is applied to step 3) in part hydrophobic Catalytic Layer and/or the hydrophobic Catalytic Layer on, then place 60～120 ℃ of drying 1～10h of vacuum drying chamber, make hydrophilic Catalytic Layer, thereby make electrode;
5) with step 4) make membrane electrode after the electrode that makes and the proton exchange membrane hot pressing.
Step 3) the described oven dry in high temperature oven refers to carry out under inert atmosphere or vacuum condition.
Described dispersant is low mass molecule alcohol, and described low mass molecule alcohol can be one or more mixture of ethanol, ethylene glycol, 1,2-PD, glycerol, isopropyl alcohol.
Described fluoropolymer emulsion is polytetrafluoroethylene (PTFE) emulsion, Kynoar (PVDF) emulsion, fluorinated ethylene propylene (FEP) (FEP) emulsion, or polytrifluorochloroethylene (PCTFE) suspension.
Described fluoropolymer powder is polytetrafluoroethylene (PTFE) powder,, Kynoar (PVDF) powder, fluorinated ethylene propylene (FEP) (FEP) powder, polytrifluorochloroethylene (PCTFE) powder, or the copolymer of tetrafluoroethene and ethene (ETFE) powder.
Described conductive carbon powder can be carbon dust, graphite, fullerene (C60), acetylene black, activated carbon, carbon nano-tube, carbon nano-fiber, carbon nano-particle or its mixture.
Described porous basic unit is carbon paper or carbon cloth.
Described coating can be adopted the modes such as silk screen printing, spraying, roll extrusion or blade coating, and wherein first, second or other Catalytic Layer can adopt identical preparation method, also can adopt different preparation methods.
Compared with prior art, the present invention mainly has following advantage: 1) the present invention uses the dry process gas diffusion layers, does not use any organic solvent, preparation technology is simple, do not have microporous layers slip infiltration problem, and the microporous layers of dry process is evenly distributed without exposed macropore; 2) the close and distant water of microporous layers of the present invention is controllable, can mate with the service conditions of fuel cell; 3) the prepared gas diffusion layers evenness of the present invention is fine, and Catalytic Layer better is compounded on the gas diffusion layers, has reduced contact resistance, has improved the battery combination property; 4) composite catalytic layer structure of the present invention is because the content of the concentration of conductive ion polymer between each Catalytic Layer is different, make catalyst and the conductive ion polymer can even contact, be conducive to improve the efficient of proton conduction, improve catalyst utilization, significantly improve battery performance.
Description of drawings
Fig. 1 is fuel cell membrane electrode structure schematic diagram of the present invention, and 1 is porous basic unit, and 2 is microporous layers, and 3 is part hydrophobic Catalytic Layer, and 4 is hydrophilic Catalytic Layer;
Fig. 2 is the fuel cell membrane electrode structure schematic diagram of the another preferred embodiment of the present invention, and 1 is porous basic unit, and 2 is microporous layers, and 3 is part hydrophobic Catalytic Layer, and 4 is hydrophilic Catalytic Layer, and 5 is the hydrophobic Catalytic Layer;
Fig. 3 is according to the membrane electrode of the fuel cell of embodiment of the invention preparation and the membrane electrode performance comparison diagram of Comparative Examples, and test condition is the empty normal pressure of hydrogen, and 60 ℃ of battery temperatures, hydrogen excess coefficient are 1.2, excess air factor 2.6, saturated humidification.
Specific embodiment:
Below by embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail, but is not limited to the content of present embodiment.
Embodiment 1:
The PVDF emulsion is diluted to 3%, then carbon paper (Toray TGPH-090) is put into the emulsion that disposes and soaked 2 minutes, hair-dryer dries up after taking out, and 3 ~ 4 content to PVDF are 20% repeatedly, then puts into 200 ℃ of high temperature ovens and burns 50 minutes
Take by weighing 2gXC-72 carbon dust and 0.5gPVDF powder, put into high speed ball mill, grind 2 minutes (25000 rev/mins).It is surperficial to adopt the mode of blade coating to be applied to through the carbon paper of hydrophobic treatment the composite dry powder of handling well, carbon dust load amount 2.0mg/cm
2Then putting into 200 ℃ of high temperature ovens burnt 50 minutes.
At microporous layers surface-coated part Hydrophobic Catalyst layer (anode carrying capacity 0.2mg/cm
2, negative electrode carrying capacity 0.5mg/cm
2).Take by weighing the JohnMattheyPt/C catalyst and put into beaker, adding a small amount of deionized water soaks catalyst, press 30ml absolute ethyl alcohol/g catalyst and add absolute ethyl alcohol, ultrasonicly mix and stir 10 minutes slips and be the ink shape, then according to Pt/C: PVDF (dry weight)=3: 1, take by weighing the PVDF emulsion and be added in the slip, continue ultrasonic and stirred 30 minutes, in 90～95 ℃ hot water, fully stirred 5 minutes after evenly.The slip for preparing adopts the mode of silk screen coating to be applied on the diffusion layer that has prepared, and then puts into 200 ℃ of high temperature ovens and burns after 30 minutes, makes Catalytic Layer.Take by weighing 20% sulfonated polyether-ether-ketone solution 300mg, according to proton conductor solution: the weight ratio of dispersant=1: 1 adds isopropyl alcohol, ultrasonic mixing 30 minutes is to fully evenly, vacuum degree be under the 0.02MPa with spray gun spraying on above-mentioned Catalytic Layer to the part layer thickness of surging be 15 μ m, then these intermediate products are positioned in the vacuum drying chamber 80 ℃ of dryings 4 hours, finish the preparation of part hydrophobic Catalytic Layer.
As previously mentioned Pt/C catalyst and absolute ethyl alcohol are mixed into uniform sizing material, according to Pt/C: conductive ion polymer resin dry weight=1: 1, the conducting polymer resin solution that takes by weighing S-PEEK is added drop-wise in the above-mentioned slip, and ultrasonic agitation 30 minutes obtains available slip.Be with spray gun above-mentioned slip to be divided to spray to for three times in part hydrophobic Catalytic Layer under 0.02～0.03MPa to obtain the hydrophilic Catalytic Layer that thickness is 1 μ m in vacuum degree, and in vacuum drying chamber 80 ℃ of dryings 4 hours, finish the electrode preparation, its structure as described in Figure 1.
The electrode and the proton exchange membrane hot pressing that prepare are obtained membrane electrode and carries out the monocell test, the results are shown in shown in Figure 3.
Embodiment 2:
The PTFE emulsion is diluted to 3%, then carbon cloth (NOK, H2315) is put into the emulsion that disposes and soaked 2 minutes, hair-dryer dries up after taking out, and 3～4 content to PTFE are 20% repeatedly, then puts into 350 ℃ of high temperature ovens and burns 50 minutes.
Take by weighing 5g carbon nano-fiber and 1.5gPTFE powder, put into high speed ball mill, grind 1 minute (20000 rev/mins).It is surperficial to adopt the mode of electrostatic spraying and roll extrusion to be applied to through the carbon paper of hydrophobic treatment the composite dry powder of handling well, carbon dust load amount 3.0mg/cm
2Then putting into 350 ℃ of high temperature ovens burnt 50 minutes.
At microporous layers surface-coated Hydrophobic Catalyst layer (anode carrying capacity 0.1mg/cm
2, negative electrode carrying capacity 0.4mg/cm
2).Take by weighing the JohnMattheyPt/C catalyst and put into beaker, adding a small amount of deionized water soaks catalyst, press 50ml isopropyl alcohol/g catalyst and add isopropyl alcohol, ultrasonicly mix and stir 10 minutes slips and be the ink shape, then according to Pt/C: PTFE (dry weight)=2: 1, take by weighing the PTFE emulsion and be added in the slip, continue ultrasonic and stirred 30 minutes, in 90～95 ℃ hot water, fully stirred 5 minutes after evenly.The slip for preparing adopts the mode of silk screen coating to be applied on the diffusion layer that has prepared, and then puts into lower 350 ℃ of high temperature oven nitrogen protection and burns 30 minutes.
In above-mentioned intermediate products preparation part hydrophobic Catalytic Layer.Take by weighing PtRuC (Tanaka's noble metal) catalyst and and 50gl, 2-mixed with propylene glycol ultrasonic agitation is even, then according to Pt/C: PTFE (dry weight)=5: 1, take by weighing the PTFE emulsion and be added in the slip, continue ultrasonic and stir to obtain distributed slurry in 30 minutes.Adopt silk screen printing that slip is applied on the hydrophobic Catalytic Layer, put into lower 350 ℃ of high temperature oven nitrogen protection and burnt 30 minutes.Take by weighing 5% Nafion solution 300mg, according to proton conductor solution: the weight ratio of dispersant=1: 1 adds absolute ethyl alcohol, ultrasonic mixing 30 minutes is to fully evenly, vacuum degree be under the 0.02MPa with spray gun spraying on part hydrophobic Catalytic Layer, then these intermediate products are positioned in the vacuum drying chamber 80 ℃ of dryings 4 hours, finish the preparation of part hydrophobic Catalytic Layer.
As previously mentioned with Pt/C catalyst and 1, the 2-mixed with propylene glycol becomes uniform sizing material, according to Pt/C: conductive ion polymer resin dry weight=1: 1, the conducting polymer resin solution that takes by weighing Nafion is added drop-wise in the above-mentioned slip, ultrasonic agitation 30 minutes obtains available slip.Be with spray gun above-mentioned slip to be divided to spray to for three times in part hydrophobic Catalytic Layer under the 0.03MPa to obtain hydrophilic Catalytic Layer in vacuum degree, and in vacuum drying chamber 80 ℃ of dryings 4 hours, finish the electrode preparation, its structure as described in Figure 2.
The electrode and the proton exchange membrane hot pressing that prepare are obtained membrane electrode and carries out the monocell test, the results are shown in shown in Figure 3.
Embodiment 3:
The PTFE emulsion is diluted to 1%, then carbon paper (Toray TGPH-090) is put into the emulsion that disposes and soaked 2 minutes, dry in the baking oven after taking out, 5 ~ 6 content to PTFE are 50% repeatedly, then put into 350 ℃ of high temperature ovens and burn 50 minutes
Take by weighing 5g acetylene black and 1.5gPTFE powder, put into high speed ball mill, grind 1 minute (20000 rev/mins).It is surperficial to adopt the mode of electrostatic spraying and roll extrusion to be applied to through the carbon paper of hydrophobic treatment the composite dry powder of handling well, acetylene black load amount 1.0mg/cm
2Then putting into 350 ℃ of high temperature ovens burnt 50 minutes.
At microporous layers surface-coated Hydrophobic Catalyst layer (anode carrying capacity 0.1mg/cm
2, negative electrode carrying capacity 0.4mg/cm
2).Take by weighing the JohnMattheyPt/C catalyst and put into beaker, adding a small amount of deionized water soaks catalyst, press 50ml ethylene glycol/g catalyst and add isopropyl alcohol, ultrasonicly mix and stir 10 minutes slips and be the ink shape, then according to Pt/C: PTFE (dry weight)=5: 1, take by weighing the PTFE emulsion and be added in the slip, continue ultrasonic and stirred 30 minutes, in 90～95 ℃ hot water, fully stirred 10 minutes after evenly.The slip for preparing adopts the mode of silk screen coating to be applied on the diffusion layer that has prepared, and then puts into lower 350 ℃ of high temperature oven nitrogen protection and burns 30 minutes.
In above-mentioned intermediate products preparation part hydrophobic Catalytic Layer.Take by weighing PtC (Tanaka's noble metal) catalyst and mix ultrasonic agitation with 50g ethylene glycol even, then according to Pt/C: PTFE (dry weight)=5: 1, take by weighing the PTFE emulsion and be added in the slip, continue ultrasonic and stir to obtain distributed slurry in 30 minutes.Adopt silk screen printing that slip is applied on the hydrophobic Catalytic Layer, put into lower 350 ℃ of high temperature oven nitrogen protection and burnt 30 minutes.Take by weighing 5% Nafion solution 300mg, according to proton conductor solution: the weight ratio of dispersant=1: 1 adds ethylene glycol, ultrasonic mixing 30 minutes is to fully evenly, vacuum degree be under the 0.05MPa with spray gun spraying on part hydrophobic Catalytic Layer, then these intermediate products are positioned in the vacuum drying chamber 80 ℃ of dryings 8 hours, finish the preparation of part hydrophobic Catalytic Layer.
As previously mentioned PtAu/C catalyst and ethylene glycol are mixed into uniform sizing material, according to PtAu/C: conductive ion polymer resin dry weight=3: 1, the conducting polymer resin solution that takes by weighing Nafion is added drop-wise in the above-mentioned slip, and ultrasonic agitation 30 minutes obtains available slip.Be with spray gun above-mentioned slip to be divided to spray to for three times in part hydrophobic Catalytic Layer under the 0.02MPa to obtain hydrophilic Catalytic Layer in vacuum degree, and in vacuum drying chamber 80 ℃ of dryings 4 hours, finish the electrode preparation, its structure as described in Figure 2.
The electrode and the proton exchange membrane hot pressing that prepare are obtained membrane electrode and carries out the monocell test, the results are shown in shown in Figure 3.
Embodiment 4:
PCTFE suspension is diluted to 10%, then carbon paper (Toray TGPH-090) being put into the emulsion that disposes soaked 2 minutes, hair-dryer dries up after taking out, and 2～3 content to PCTFE are 40% repeatedly, then puts into 300 ℃ of high temperature ovens and burns 30 minutes.
Take by weighing 2g nano-carbon powder and 0.5gPCTFE powder, put into high speed ball mill, grind 5 minutes (30000 rev/mins).It is surperficial to adopt the mode of blade coating to be applied to through the carbon paper of hydrophobic treatment the composite dry powder of handling well, carbon dust load amount 1.2mg/cm
2Then putting into 300 ℃ of high temperature ovens burnt 30 minutes.
At microporous layers surface-coated part Hydrophobic Catalyst layer (anode carrying capacity 0.5mg/cm
2, negative electrode carrying capacity 0.8mg/cm
2).Take by weighing the JohnMattheyPt/C catalyst and put into beaker, adding a small amount of deionized water soaks catalyst, press 30ml absolute ethyl alcohol/g catalyst and add absolute ethyl alcohol, ultrasonicly mix and stir 10 minutes slips and be the ink shape, then according to Pt/C: PTFE (dry weight)=4: 1, take by weighing the PTFE emulsion and be added in the slip, continue ultrasonic and stirred 30 minutes, in 90～95 ℃ hot water, fully stirred 5 minutes after evenly.The slip for preparing adopts the mode of silk screen coating to be applied on the diffusion layer that has prepared, and then puts into 350 ℃ of high temperature ovens and burns 30 minutes, makes Catalytic Layer.Take by weighing 10% SPSF solution 100mg, according to proton conductor solution: the weight ratio of dispersant=1: 1 adds 1, the 2-propylene glycol, ultrasonic mixing 30 minutes is to fully evenly, vacuum degree be under the 0.02MPa with spray gun spraying on above-mentioned Catalytic Layer, then these intermediate products are positioned in the vacuum drying chamber 80 ℃ of dryings 4 hours, finish the preparation of part hydrophobic Catalytic Layer.
As previously mentioned PtFe/C catalyst and absolute ethyl alcohol are mixed into uniform sizing material, according to PtFe/C: conductive ion polymer resin dry weight=1: 1, the conducting polymer resin solution that takes by weighing S-PS is added drop-wise in the above-mentioned slip, and ultrasonic agitation 30 minutes obtains available slip.Be with spray gun above-mentioned slip to be divided to spray to for three times in part hydrophobic Catalytic Layer under 0.02～0.03MPa to obtain hydrophilic Catalytic Layer in vacuum degree, and in vacuum drying chamber 80 ℃ of dryings 8 hours, finish the electrode preparation, its structure as described in Figure 1.
The electrode and the proton exchange membrane hot pressing that prepare are obtained membrane electrode.
Embodiment 5:
The PTFE emulsion is diluted to 20%, then carbon cloth (NOK, H2315) is put into the emulsion that disposes and soaked 2 minutes, hair-dryer dries up after taking out, and 2～3 content to PTFE are 60% repeatedly, then puts into 380 ℃ of high temperature ovens and burns 10 minutes.
Take by weighing 10g graphite and fullerene, 0.5gETFE powder, put into high speed ball mill, grind 5 minutes (30000 rev/mins).It is surperficial to adopt the mode of blade coating to be applied to through the carbon cloth of hydrophobic treatment the composite dry powder of handling well, carbon dust load amount 1.2mg/cm
2, then put into 380 ℃ of high temperature ovens and burnt 60 minutes, make gas diffusion layers.
The preparation of part hydrophobic Catalytic Layer and hydrophilic Catalytic Layer is with embodiment 4.
The electrode and the proton exchange membrane hot pressing that prepare are obtained membrane electrode.
Embodiment 6:
The preparation of gas diffusion layers is with embodiment 1.
Take by weighing the JohnMattheyPt/C catalyst and put into beaker, adding a small amount of deionized water soaks catalyst, press 1ml glycerol/g catalyst and add glycerol, ultrasonicly mix and stir 1 minute slip and be the ink shape, then according to Pt/C: FEP (dry weight)=1: 1, take by weighing the FEP emulsion and be added in the slip, continue ultrasonic and stirred 60 minutes, in 90～95 ℃ hot water, fully stirred 5 minutes after evenly.The slip for preparing adopts the mode of silk screen coating to be applied on the diffusion layer that has prepared, and then puts into high temperature oven, burns 10 minutes under 400 ℃, nitrogen atmosphere, makes Catalytic Layer.Take by weighing 10% SPSF solution 100mg, according to proton conductor solution: the weight ratio of dispersant=1: 5 adds isopropyl alcohol, ultrasonic mixing 30 minutes is to fully evenly, vacuum degree be under the 0.02MPa with spray gun spraying on above-mentioned Catalytic Layer to part water-repellent layer thickness be 5 μ m, then these intermediate products are positioned in the vacuum drying chamber 60 ℃ of dryings 10 hours, finish the preparation of part hydrophobic Catalytic Layer.
As previously mentioned PtFe/C catalyst and absolute ethyl alcohol are mixed into uniform sizing material, according to PtFe/C: conductive ion polymer resin dry weight=5: 1, take by weighing SPSF solution and be added drop-wise in the above-mentioned slip, ultrasonic agitation 60 minutes obtains available slip.Be with spray gun above-mentioned slip to be divided to spray to for three times in part hydrophobic Catalytic Layer under the 0.02MPa to obtain the hydrophilic Catalytic Layer that thickness is 3 μ m in vacuum degree, and in vacuum drying chamber 120 ℃ of dryings 1 hour, finish the electrode preparation, its structure as described in Figure 1.
The electrode and the proton exchange membrane hot pressing that prepare are obtained membrane electrode.
Embodiment 7:
The preparation of gas diffusion layers is with embodiment 1.
Take by weighing the JohnMattheyPt/C catalyst and put into beaker, adding a small amount of deionized water soaks catalyst, press 15ml1,2-propylene glycol/g catalyst adds 1,2-PD, ultrasonicly mixes and stirs 15 minutes slips and be the ink shape, then according to Pt/C: FEP (dry weight)=10: 1, take by weighing the FEP emulsion and be added in the slip, continue ultrasonic and stirred 45 minutes, in 90～95 ℃ hot water, fully stirred 5 minutes after evenly.The slip for preparing adopts the mode of silk screen coating to be applied on the diffusion layer that has prepared, and then puts into high temperature oven, burns 60 minutes under 150 ℃, vacuum condition, makes Catalytic Layer.Take by weighing 10% SPSF solution 100mg, according to proton conductor solution: the weight ratio of dispersant=1: 3 adds glycerol, ultrasonic mixing 30 minutes is to fully evenly, vacuum degree be under the 0.02MPa with spray gun spraying on above-mentioned Catalytic Layer to part water-repellent layer thickness be 10 μ m, then these intermediate products are positioned in the vacuum drying chamber 120 ℃ of dryings 1 hour, finish the preparation of part hydrophobic Catalytic Layer.
As previously mentioned PtFe/C catalyst and 1,2-PD are mixed into uniform sizing material, according to PtFe/C: conductive ion polymer resin dry weight=2: 1, take by weighing SPSF solution and be added drop-wise in the above-mentioned slip, ultrasonic agitation 50 minutes obtains available slip.Be with spray gun above-mentioned slip to be divided to spray to for three times in part hydrophobic Catalytic Layer under the 0.02MPa to obtain the hydrophilic Catalytic Layer that thickness is 1 μ m in vacuum degree, and in vacuum drying chamber 60 ℃ of dryings 10 hours, finish the electrode preparation, its structure as described in Figure 1.
The electrode and the proton exchange membrane hot pressing that prepare are obtained membrane electrode.
Embodiment 8:
The FEP emulsion is diluted to 1%, then carbon cloth (NOK, H2315) is put into the emulsion that disposes and soaked 2 minutes, hair-dryer dries up after taking out, and 2～3 content to FEP are 5% repeatedly, then puts into 260 ℃ of high temperature ovens and burns 60 minutes.
Take by weighing 1g activated carbon and carbon nano-tube, 1gFEP powder, put into high speed ball mill, grind 5 minutes (30000 rev/mins).It is surperficial to adopt the mode of blade coating to be applied to through the carbon cloth of hydrophobic treatment the composite dry powder of handling well, carbon dust load amount 1.2mg/cm
2, then put into 230 ℃ of high temperature ovens and burnt 45 minutes, make gas diffusion layers.
The preparation of part hydrophobic Catalytic Layer and hydrophilic Catalytic Layer is with embodiment 7.
The electrode and the proton exchange membrane hot pressing that prepare are obtained membrane electrode.
Comparative example:
Adopt wet method to prepare microporous layers, take by weighing 5g carbon black (Vulcan XC-72), add 100g1, the 2-propylene glycol, ultrasonic wave disperseed 30 minutes after slowly stirring, the PTFE emulsion that adds again 10g 20wt%, slowly stir under the frozen water cooling condition ultrasonic dispersion 30 minutes at glass bar, then be applied to the carbon paper surface with silk screen, 365 ℃ of dryings, make microporous layers, the upper carrying capacity of Vulcan XC-72 is that negative electrode is 1.5mg/cm
2Anode 1.7mg/cm
2
Catalytic Layer adopts traditional hydrophobic electrode, at gas diffusion layers surface-coated pt/C catalyst layer (anode carrying capacity 0.4mg/cm
2, negative electrode carrying capacity 0.9mg/cm
2), and spraying Nafion solution carries out three-dimensional and forms electrode, then with hot press clamping proton membrane in the middle of the anode and cathode is hot pressed into MEA, tests its performance, as shown in Figure 3.
Claims (10)
1. the membrane electrode of a fuel cell comprises gas diffusion layers and Catalytic Layer, it is characterized in that described Catalytic Layer is multi-layer compound structure, and described multi-layer compound structure is coated with hydrophilic Catalytic Layer for to be coated with part hydrophobic Catalytic Layer at gas diffusion layers on it; Described part hydrophobic Catalytic Layer mainly is comprised of the first catalyst, hydrophober and conductive ion polymer; Described hydrophilic Catalytic Layer mainly is comprised of the second catalyst and conductive ion polymer; The content of described conductive ion polymer between each Catalytic Layer is different.
2. the membrane electrode of fuel cell according to claim 1, the thickness that it is characterized in that described part hydrophobic Catalytic Layer is 5～15 μ m, the thickness of described hydrophilic Catalytic Layer is 1～5 μ m.
3. the membrane electrode of fuel cell according to claim 1 is characterized in that described conductive ion polymer is perfluorinated sulfonic acid resin or polyether-ether-ketone, the polysulfones processed through oversulfonate.
4. the membrane electrode of fuel cell according to claim 1 is characterized in that described hydrophober is ptfe emulsion, Kynoar emulsion, fluorinated ethylene propylene (FEP) emulsion or polytrifluorochloroethylene suspension.
5. the preparation method of a fuel cell membrane electrode is characterized in that adopting following steps to make:
1) porous basic unit is immersed fully wetting in the fluoropolymer emulsion of 1%～20wt% after, take out dry; Repeat above-mentioned steps until the content of fluoropolymer reaches 5%～60wt%, then 200～380 ℃ of heat treatment 10～60min in high temperature oven;
2) take by weighing conductive carbon powder and the fluoropolymer powder that mass ratio is 10:0.5-10, the high speed ball milling mixes, obtain composite powder, then composite powder is applied in the porous basic unit, make microporous layers, thereby make gas diffusion layers, then the gas diffusion layers that makes is placed 200～380 ℃ of heat treatment 10～60min of high temperature oven;
3) catalyst is mixed with the mass ratio of low mass molecule alcohol according to 1:1～50, behind ultrasonic agitation 1～20min, make ink shape slip, then be that the mass ratio of 1～10:1 adds hydrophober in above-mentioned slip according to catalyst/hydrophober, then behind ultrasonic agitation 30～60min, be applied to step 2) on the gas diffusion layers of preparation, then in high temperature oven, behind 150～400 ℃ of lower burning 10～60min, make Catalytic Layer; Be after the mass ratio of 1:1～5 mixes, to be applied on the above-mentioned Catalytic Layer according to conductive ion polymer/dispersant, then place 60～120 ℃ of drying 1～10h of vacuum drying chamber, make part hydrophobic Catalytic Layer;
4) catalyst is mixed with the mass ratio of low mass molecule alcohol according to 1:1～50, make slip, be that the mass ratio of 1～5:1 adds the conductive ion polymer in above-mentioned slip according to catalyst/conductive ion polymer then, behind ultrasonic agitation 30～60min, make mixed slurry, then above-mentioned mixed slurry is applied on the part hydrophobic Catalytic Layer in the step 3), then place 60～120 ℃ of drying 1～10h of vacuum drying chamber, make hydrophilic Catalytic Layer, thereby make electrode;
5) make membrane electrode after the electrode that step 4) is made and the proton exchange membrane hot pressing.
6. the preparation method of fuel cell membrane electrode according to claim 5 is characterized in that described fluoropolymer emulsion is ptfe emulsion, Kynoar emulsion, fluorinated ethylene propylene (FEP) emulsion or polytrifluorochloroethylene suspension; Described fluoropolymer powder is the copolymer powder of polytetrafluorethylepowder powder, Kynoar powder, fluorinated ethylene propylene (FEP) powder, polytrifluorochloroethylene powder or tetrafluoroethene and ethene.
7. the preparation method of fuel cell membrane electrode according to claim 5 is characterized in that described conductive carbon powder is carbon dust, graphite, fullerene, acetylene black, activated carbon, carbon nano-tube, carbon nano-fiber, carbon nano-particle or its mixture.
8. the preparation method of fuel cell membrane electrode according to claim 5 is characterized in that described dispersant is low mass molecule alcohol.
9. the preparation method of fuel cell membrane electrode according to claim 5 is characterized in that described low mass molecule alcohol is one or more mixture of ethanol, ethylene glycol, 1,2-PD, glycerol, isopropyl alcohol.
10. the preparation method of fuel cell membrane electrode according to claim 5 is characterized in that described porous basic unit is carbon paper or carbon cloth.
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| CN102104155B (en) * | 2009-12-18 | 2014-04-02 | 中国科学院大连化学物理研究所 | Low-platinum cathode catalyst layer used for fuel cell and application thereof |
| CN104577138A (en) * | 2014-12-12 | 2015-04-29 | 浙江工业大学 | Direct methanol fuel cell membrane electrode structure and preparation method thereof |
| CN104608438B (en) * | 2014-12-31 | 2016-08-24 | 国核电力规划设计研究院 | A kind of Super hydrophobic compound film and preparation method |
| CN106477520A (en) * | 2015-08-24 | 2017-03-08 | 李国锋 | A kind of proton energy parent rock amorphous nanometer composite material |
| CN107123822B (en) * | 2017-05-08 | 2019-07-19 | 中科院大连化学物理研究所张家港产业技术研究院有限公司 | A kind of preparation method of used in proton exchange membrane fuel cell gas diffusion layers |
| CN108321414A (en) * | 2018-03-09 | 2018-07-24 | 黄河科技学院 | A kind of hydrophobic processing method of fuel cell supporting layer |
| CN108842162A (en) * | 2018-06-15 | 2018-11-20 | 重庆大学 | For electrochemical reduction CO2SnO2Nanometer sheet gas-diffusion electrode and method |
| CN109346728A (en) * | 2018-09-25 | 2019-02-15 | 中新国际联合研究院 | Non-precious metal catalytic electrode, membrane electrode and preparation method thereof |
| 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 |
| CN111384422B (en) * | 2018-12-28 | 2023-02-28 | 博西华电器（江苏）有限公司 | Redox device, gas conditioning system and refrigeration appliance |
| CN110504472B (en) * | 2019-07-16 | 2021-11-09 | 江苏大学 | Direct methanol fuel cell membrane electrode for improving catalyst utilization rate and preparation method thereof |
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| CN114204084B (en) * | 2021-11-26 | 2023-12-22 | 大连理工大学 | Method for constructing hollow fiber type proton exchange membrane fuel cell by electrospinning |
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