CN101114713B - Fuel cell gaseous diffusion layer and process for producing fuel cell electrode and membrane electrode - Google Patents
Fuel cell gaseous diffusion layer and process for producing fuel cell electrode and membrane electrode Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
A preparation method for a fuel cell gas diffusion layer, comprising that the slurry with conductive agents and hydrophobic agents is evenly distributed onto support materials and the support materials with conductive agents and hydrophobic agents are sintered, the invention is characterized in that the method that the slurry with conductive agents and hydrophobic agents is evenly distributed onto support materials comprises that a pressure difference is formed on a first surface and a second surface of the supporting materials, the pressure on the second surface is larger than the pressure on the first surface, and the slurry with conductive agents and hydrophobic agents is contacted with the second surface of the supporting materials, the first surface and the second surface are respectively the two opposite surfaces of the supporting materials. The method provided by the invention has less operation steps and a simple process, and the diffusion layer which protects almost absolutely the porosity of the supporting materials can be obtained without extra open cell agents, and thus, the current density of the battery is nearly 43 percent higher than similar batteries.
Description
Technical field
The invention relates to a kind of preparation method of fuel battery gas diffusion layer and comprise the electrode and the membrane electrode preparation method of gas diffusion layers obtained by this method.
Background technology
Fuel cell is a kind of device that produces electric energy by oxidizing gas generation electrochemical reactions such as fuel and oxygen or air, this battery has energy conversion efficiency height, simple in structure, advantages such as noise is low, fuel source is abundant, non-environmental-pollution, thereby be with a wide range of applications, be one of following ideal source.Fuel cell can be used for the electrical source of power of small portable power supply, family's small hydropower station, electric automobile, submarine etc.
In fuel cell, the membrane electrode of the battery core parts that act as a fuel comprises proton exchange membrane and is positioned at the electrode of proton exchange membrane both sides.Electrode is a kind of gas-diffusion electrode, comprise gas diffusion layers and the Catalytic Layer that loads on the gas diffusion layers, gas diffusion layers comprises backing material and the diffusion layer that loads on the backing material, backing material is generally charcoal fiber, carbon cloth, carbon paper and the various expanded metal of conduction, the water-repelling agent that generally contain diffusion layer graphite agent and selectivity contain, water-repelling agent generally can be polytetrafluoroethylene, hexafluoropropylene, Kynoar.The catalyst of Catalytic Layer be generally platinum powder end, platiniferous alloy powder, load on the platinum on the carrier or load on the alloy powder of the platiniferous on the carrier.The alloy of described platiniferous contains platinum and is selected from ruthenium, tin, iridium, osmium, the rhenium one or more.Described carrier is to have the higher specific surface and the carrier of conduction, as active carbon.Proton exchange membrane is a kind of permeable air-locked pellicle, and it has the proton conduction effect, can also prevent oxidant and fuel generation mixed explosion.
The gas diffusibility of gas diffusion layers (being the porosity of diffusion layer) has significant effects to the chemical property of fuel cell, so fuel cell has higher requirement to the gas diffusibility of gas diffusion layers.Simultaneously, in order to satisfy the commercial requirement of fuel cell, it is simple that the manufacture craft of membrane electrode is wanted, and the battery performance of membrane electrode assembling is good thus.
In order to satisfy above-mentioned two requirements as far as possible, the preparation technology to gas diffusion layers had carried out research extensively and profoundly in recent years.At present the preparation method of the gas diffusion layers of comparative maturity comprises and soaks carbon paper repeatedly with ptfe emulsion earlier and dry up, and the slurry that carbon black, polytetrafluoroethylene and solvent are formed is coated on the carbon paper then, makes gas diffusion layers after baking.Gas diffusion layers combined with Catalytic Layer promptly make fuel cell electrode, this fuel cell electrode and proton exchange membrane hot pressing are formed membrane electrode.
Preparation method's ratio of above-mentioned gas diffusion layer is easier to operation, but can not guarantee surfacing by the diffusion layer that said method makes, especially it is uneven to dry the rear surface, make gas diffusion layers descend with the utilance that causes catalyst after Catalytic Layer combines, also make simultaneously and loose contact between Catalytic Layer and the proton exchange membrane interface influence the membrane electrode performance; In addition, adopt the method that applies to cause that easily the raw material of wood-charcoal material stops up the problem of the pore on the carbon paper, causes the gaseous diffusion performance of gas diffusion layers bad.
Gaseous diffusion efficient when improving operation of fuel cells need take the whole bag of tricks to improve the porosity of fuel battery gas diffusion layer, is beneficial to gaseous diffusion.In addition, the hole of gas diffusion layers can not be too big, must be small pore, could guarantee that the catalyst in the Catalytic Layer can not enter the opposite side of carbon paper by carbon paper, influences catalytic effect.
CN1658422A discloses a kind of preparation method of fuel battery gas diffusion layer, this method comprises: the preliminary treatment of (1) porous substrate: the base material of porous was placed in the water-repelling agent of 10-25 weight % concentration 5-10 minute, take out then and in air, dry 10-20 minute, be placed on again in the 340-360 ℃ of stove and heated 10-30 minute; (2) preparation of microporous layers slip: a) take by weighing carbon black and boiling point be 80-120 ℃ solvent with 1: the weight ratio of 10-50 is mixed and was stirred 30-120 minute; B) then with the weight ratio carbon black: water-repelling agent 1: 0.01-1 adds water-repelling agent, stirs 5-60 minute; (3) preparation of mixed liquor: the microporous layers slip evenly is divided into 2-10 part, with the weight ratio carbon black: pore former=1: 0.5-8 adds pore former, the addition of pore former gradient is successively successively decreased, form 2-10 kind mixed solution, every kind of mixed liquor continues to stir 60-120 minute, takes out after ultrasonic 10-30 minute standby; Adopt rubbing method, spraying, rolling process, spraying, print process or rubbing method compound 2-10 kind mixed liquor to be compounded on the pretreated porous substrate then by 2-10 time, compound order is undertaken compound by the order that the content of pore former in the mixed liquor successively decreases successively, the highest mixed liquor of the compound pore-forming agent content first time, the stove sintering of putting into 340-360 ℃ at last obtained gas diffusion layers in 10-30 minute.Three-in-one (EMAS) combines with this gas diffusion layers and membrane electrode, forms membrane electrode (MEA).Described membrane electrode is three-in-one to be the proton exchange membrane that two surfaces all have Catalytic Layer.
The procedure complexity of this preparation fuel battery gas diffusion layer, the step of coating porosity too many, diffusion layer can not get good assurance, are unfavorable for the mass and the industrialization of membrane electrode.And the needed membrane electrode of assembling film electrode three-in-one (EMAS) proton exchange membrane in the preparation shrinks easily, thereby makes film wrinkling, and is very unfavorable to the membrane electrode performance of preparation, makes that the current density of fuel cell is low.
Summary of the invention
An object of the present invention is for the low shortcoming of current density that fuel battery gas diffusion layer gaseous diffusion performance difference that prior art makes causes fuel cell, the preparation method who provides a kind of gaseous diffusion performance can make the fuel battery gas diffusion layer that the fuel cell current density is high well are provided.
Another object of the present invention provides a kind of preparation method who comprises the fuel cell electrode of above-mentioned gas diffusion layer.
The 3rd purpose of the present invention provides a kind of preparation method who comprises the fuel cell membrane electrode of above-mentioned gas diffusion layer.
The preparation method of fuel battery gas diffusion layer provided by the invention comprises that the slurry that will contain conductive agent and water-repelling agent is evenly distributed on the backing material, sintering contains the backing material of conductive agent and water-repelling agent then, it is characterized in that, first surface and second surface that the slurry that will contain conductive agent and water-repelling agent the method on the backing material of being evenly distributed to is included in backing material form pressure differential, the pressure of second surface is greater than the pressure of first surface, the slurry that will contain conductive agent and water-repelling agent contacts with the second surface of backing material, and first surface is respectively two relative surfaces of backing material with second surface.
The preparation method of fuel cell electrode provided by the invention is included in supported catalyst layer on the gas diffusion layers, and wherein, described gas diffusion layers adopts method preparation provided by the invention.
The preparation method of fuel cell membrane electrode provided by the invention comprise with two fuel cell electrodes respectively with two surface combination of proton exchange membrane, wherein, described fuel cell electrode adopts method preparation provided by the invention.
The preparation method of fuel cell membrane electrode provided by the invention comprises two surface combination that two gas diffusion layers had the proton exchange membrane of Catalytic Layer respectively with the surface, and wherein, described gas diffusion layers adopts method preparation provided by the invention.
Method operating procedure provided by the invention is few, process is simple, the diffusion layer that obtains almost absolutely keeps the porosity of backing material itself, thereby only need select the proper supporting material, can make and have corresponding porosity and the diffusible gas diffusion layers of gas, make the similar battery of current density ratio of fuel cell improve nearly 43%.In addition, preparation method of the present invention does not need the porosity and the gas diffusibility that additionally use pore-creating agent can guarantee gas diffusion layers, can save cost on the one hand, can also avoid the adverse effect of being brought by pore-creating agent to battery on the other hand.
Description of drawings
Fig. 1 is the front view of suction filtration device among the present invention;
Fig. 2 be among Fig. 1 the suction filtration device along the profile of A-A direction;
Fig. 3 is the three-dimensional effect diagram of suction filtration device among Fig. 1;
The battery performance figure of the fuel cell that Fig. 4 makes for the embodiment of the invention 1,2 and comparative example 1.
Embodiment
According to the present invention, described formation pressure difference method can be the first surface one side suction filtration from backing material.The concrete operations of described suction filtration can be adopted the method that is similar to funnel suction filtration solidliquid mixture, comprise backing material is put into the suction filtration device, the first surface of backing material is contacted with the suction filtration device, the slurry that will contain conductive agent and water-repelling agent is then poured on the second surface of backing material, carry out suction filtration from first surface one side of backing material then, make on the second surface of slurry attached to backing material, described first surface is respectively two relative surfaces of backing material with second surface, can guarantee that like this slurry evenly is attached to the non-porose area of backing material, can guarantee that again the hole district of backing material is not blocked.The pressure of described suction filtration is as long as guarantee that backing material tangible slurry can not take place leaks, gas diffusion layers backing material for routine, preferred described pressure differential is the 0.01-0.1 MPa, 0.01-0.09 MPa more preferably, and the time chien shih slurry thin layer of suction filtration is not taken out to be split.More preferably when beginning earlier with less pressure suction filtration, and then under bigger constant pressure suction filtration.
Described suction filtration device can be to have the various devices that are similar to the Buchner funnel structure, promptly has the device that side edge and bottom are evenly distributed with aperture, for example can be the suction filtration device shown in Fig. 1-3.The porosity of described suction filtration device is preferably 200-1000 hole/square centimeter greater than the porosity of backing material, and the size in hole is preferably the 0.001-0.005 square centimeter.
The impouring amount of described slurry decides according to required gaseous diffusion layer thickness, and under the preferable case, the impouring amount of described slurry makes conductive agent and water-repelling agent form the thin layer that thickness is the 50-200 micron on backing material.Under the preferable case, the weight ratio of conductive agent and water-repelling agent is 1-100 in the described slurry: 1, be preferably 1-10: and 1,1-8 more preferably: 1,1.5-6 more preferably: 1.
Under the preferable case, the preparation method of gas diffusion layers provided by the invention also is included in and forms before the pressure differential, earlier the part slurry is distributed on the backing material equably in advance, obtains having the backing material of pasty film.There is no particular limitation to the thickness of described film, and preferred film can cover the second surface of backing material fully.The pre-slurry that distributes does not carry out suction filtration, the film of Xing Chenging not only covers the non-porose area of backing material like this, also cover simultaneously the hole district of backing material, slurry can prevent further that disposed slurry from flowing out and cause slurry loss with contacting at such film surface from the hole of backing material.More preferably under the situation, this method comprises that also the backing material to having pasty film carries out presintering, and the temperature of sintering is 340-400 ℃, and the time of sintering is 20-90 minute.Sintering finishes after the cooling again, and impouring forms the required remaining slurry of pulp layer.
More preferably under the situation, before this method also is included in the slurry that will contain conductive agent and water-repelling agent and the second surface of backing material contacts, will soak in backing material water-repelling agent solution or the emulsion earlier.The concentration of described water-repelling agent solution or emulsion is 5-30 weight %, and the time of immersion is 10-70 minute.The mode of described immersion is preferably soaks 2-7 time, each 5-10 minute, dries earlier before each the immersion.Dry and help to make water-repelling agent fully to enter in the backing material, thereby improve the hydrophobicity of gas diffusion layers.More preferably under the situation, finish above-mentioned repeatedly soak after, also with backing material at 310-380 ℃ of sintering temperature 10-70 minute.
Further, before method provided by the invention preferably also is included in the slurry that will contain conductive agent and water-repelling agent and the second surface of backing material contacts, backing material is carried out presintering, the temperature of sintering is preferably 300-500 ℃, more preferably 340-400 ℃, the time of sintering is preferably 10-120 minute, more preferably 20-90 minute.Can remove the impurity that is adsorbed in the backing material by sintering, thereby avoid the influence that causes by the impurity in the backing material battery performance.Presintering more preferably described herein distributes in advance at the slurry that above-mentioned selectivity comprises, water-repelling agent solution or emulsion are carried out before soaking.
According to the present invention, described water-repelling agent can be the conventional various water-repelling agents that use of fuel cell field, for example can be in polytetrafluoroethylene, polyhexafluoropropylene, the Kynoar one or more.Described backing material can be the 100-500 hole/carbon paper of square centimeter, carbon cloth, expanded metal for porosity, and described conductive agent is preferably carbon black or conductive acetylene is black.The solvent of described formation slurry and water-repelling agent solution or emulsion can be identical or inequality, for example can be independently selected from ethanol, isopropyl alcohol, ethylene glycol, the water one or more respectively.
Described sintering to the backing material that contains conductive agent and water-repelling agent comprises backing material that second surface is formed with the slurry thin layer 300-400 ℃ of heating 5-100 minute down, more preferably 310-380 ℃ of heating 10-70 minute down.
Preparation method according to fuel cell electrode provided by the invention, wherein Catalytic Layer can adopt the conventional various Catalytic Layer of using of fuel cell field, can load on the gas diffusion layers then and obtains by catalyst, solvent, Nafion solution being mixed with slurry.The method of described load can be spraying, silk screen print method, rubbing method, rolling process, print process, casting method.The weight ratio of described catalyst, solvent and Nafion solution is preferably (1-20): (5-50): (1-10).Described catalyst can be for the alloy powder of the commonly used various catalyst of fuel cell such as platinum powder end, platiniferous, load on the platinum on the carrier or load on alloy powder or the cathod catalyst such as the platinum powder end of the platiniferous on the carrier or load on platinum powder end on the carrier.The alloy of described platiniferous contains platinum and is selected from ruthenium, tin, iridium, osmium, the rhenium one or more.Described carrier is carrier such as the active carbon with higher specific surface and conduction.Described solvent can be isopropyl alcohol and/or glycerol.
Preparation method according to fuel cell membrane electrode provided by the invention, the described Catalytic Layer that two fuel cell electrodes are comprised two fuel cell electrodes with the method for two surface combination of proton exchange membrane is respectively carried out hot pressing with two surfaces of proton exchange membrane after superimposed respectively, form the integrated film electrode structure, the condition optimization of hot pressing comprises that temperature is 110-150 ℃, and pressure is that 0.5-5 MPa, hot pressing time are 1-4 minute.Wherein, described proton exchange membrane can be conventional various proton exchange membrane such as Nafion112, Nafion115, Nafion117 or the Nafion1035 proton exchange membrane of using of fuel cell field.
According to another kind of membrane electrode preparation method provided by the invention, the described method of two surface combination that two gas diffusion layers are had a proton exchange membrane of Catalytic Layer with the surface respectively can comprise carries out hot pressing after two gas diffusion layers are had Catalytic Layer surperficial superimposed with two of proton exchange membrane respectively again, form the integrated film electrode structure, the condition optimization of hot pressing comprises that temperature is 110-150 ℃, and pressure is that 0.5-5 MPa, hot pressing time are 1-4 minute.The proton exchange membrane that described surface has Catalytic Layer also is common described membrane electrode three-in-one (EMAS), can be commercially available.
The following examples will the present invention is further illustrated.
Embodiment 1
Present embodiment is used to illustrate the preparation method and the preparation method of the fuel cell electrode that contains this gas diffusion layers and the preparation method of fuel cell membrane electrode of gas diffusion layers provided by the invention.
The preparation of gas diffusion layers: with fuel cell with carbon paper (TORAY090, toray company produce) 340 ℃ of sintering 90 minutes, be adsorbed on impurity in the carbon paper with removal.Prepare the ptfe emulsion of 15 weight % concentration, and then the carbon paper behind the sintering put into wherein soak 4 times, each soak to take out after 9 minutes soak again after drying next time, in 350 ℃ of stoves, be incubated 50 minutes again after soaking 4 times, be cooled to room temperature then.VXC-72 carbon black and polytetrafluoroethylene added be mixed into uniform slurry in the entry, the content of polytetrafluoroethylene is that the weight of 10 weight %, VXC-72 carbon black is 40 weight % in the slurry, and surplus is a water.On the second surface of carbon paper, be coated with the thin slurry of one deck earlier, dry the back and form carbon paper with pasty film, this carbon paper is placed on the suction filtration device shown in Figure 1, the first surface that does not wherein have the carbon paper of pasty film contacts with the suction filtration device, the size of carbon paper is big or small consistent with the suction filtration device, the bottom of suction filtration device is connected with bottle,suction by rubber stopper, the suction filtration bottle neck is connected with circulating water pump, then slurry is poured on the carbon paper, open water pump simultaneously and slowly carry out suction filtration, pressure in the bottle,suction is 0.98 MPa, slurry in the process of suction filtration attached to carbon paper on, to form thickness be 100 microns and have the thin layer of a lot of micropores to drain the back.The carbon paper that will have thin layer then is put in 370 ℃ of stoves and is incubated 20 minutes, takes out after cooling, promptly gets gas diffusion layer for fuel cell.
The preparation of fuel cell electrode: with Pt/C catalyst (Pt content is 5 weight %): isopropyl alcohol: Nafion solution is made slurry with 1: 5: 1 mixing and stirring of weight ratio.Then slurry is coated on the above-mentioned gas diffusion layers that makes by spraying process, was positioned in 80 ℃ the vacuum drying chamber baking after drying again 50 minutes in air, remove solvent, take out the cooling back.The content of Pt is 1 milligram/square centimeter in the fuel cell electrode.
The preparation of fuel cell membrane electrode: two above-mentioned fuel cell electrodes that make are alignd with the both sides of onesize proton exchange membrane Nafion112, are that 110 ℃, pressure are hot pressing 2 minutes under 4 MPas in temperature, form the integrated film electrode.
Embodiment 2
Present embodiment is used to illustrate the preparation method and the preparation method of the fuel cell electrode that contains this gas diffusion layers and the preparation method of fuel cell membrane electrode of gas diffusion layers provided by the invention.
Method according to embodiment 1 prepares fuel battery gas diffusion layer, and different is that carbon paper directly uses without sintering.
Embodiment 3
Present embodiment is used to illustrate the preparation method and the preparation method of the fuel cell electrode that contains this gas diffusion layers and the preparation method of fuel cell membrane electrode of gas diffusion layers provided by the invention.
The preparation of gas diffusion layers: with fuel cell with carbon cloth (6K Toray/127, toray company produce) 360 ℃ of sintering 70 minutes, be adsorbed on impurity in the carbon cloth with removal.Prepare the ptfe emulsion of 15 weight % concentration, and then the carbon paper behind the sintering put into wherein soak 3 times, each soak to take out after 10 minutes soak again after drying next time, in 320 ℃ of stoves, be incubated 60 minutes again after soaking 3 times, be cooled to room temperature then.Conductive acetylene is mixed into uniform slurry black the adding in the isopropanol solvent with polytetrafluoroethylene, and the weight that the content of polytetrafluoroethylene is 10 weight % in the slurry, conductive acetylene is black is 50 weight %, and surplus is an isopropyl alcohol.On the second surface of carbon paper, be coated with the thin slurry of one deck earlier, dry the back and form carbon paper with pasty film, this carbon paper is placed on the suction filtration device shown in Figure 1, the first surface that does not wherein have the carbon paper of pasty film contacts with the suction filtration device, the size of carbon paper is big or small consistent with the suction filtration device, the bottom of suction filtration device is connected with bottle,suction by rubber stopper, the suction filtration bottle neck is connected with circulating water pump, then slurry is poured on the carbon cloth, open water pump simultaneously and carry out suction filtration, pressure in the bottle,suction is 0.95 MPa, slurry in the process of suction filtration attached to carbon cloth on, drain and form thickness behind the solvent and be 200 microns and have the thin layer of a lot of micropores.The carbon paper that will have thin layer then is put in 370 ℃ of stoves and is incubated 20 minutes, takes out after cooling, promptly gets the fuel battery negative pole gas diffusion layers.
The preparation of fuel cell electrode: with Pt/C catalyst (Pt content is 20 weight %): isopropyl alcohol: Nafion solution is made slurry with 1: 7: 1 mixing and stirring of weight ratio.Then slurry is coated on the above-mentioned gas diffusion layers that makes by spraying process, was positioned in 80 ℃ the vacuum drying chamber baking after drying again 50 minutes in air, remove solvent, take out the cooling back.The content of Pt is 1 milligram/square centimeter in the fuel cell electrode.
The preparation of fuel cell membrane electrode: two above-mentioned fuel cell electrodes that make are alignd with the both sides of proton exchange membrane Nafion112, and under 110 ℃ of temperature, under 4 MPa pressure, hot pressing 2 minutes forms the integrated film electrode.
Embodiment 4
Cathode preparation method and method for preparing membrane electrode that present embodiment is used to that the preparation method of gas diffusion layers provided by the invention is described and contains this gas diffusion layers.
The preparation of gas diffusion layers: with fuel cell with carbon cloth (6K Toray/127, toray company produce) 370 ℃ of sintering 30 minutes, be adsorbed on impurity in the carbon cloth with removal.VXC-72 carbon black and polytetrafluoroethylene added be mixed into uniform slurry in the entry, the content of polytetrafluoroethylene is that the weight of 20 weight %, VXC-72 carbon black is 60 weight % in the slurry, and surplus is a water.On the second surface of carbon cloth, be coated with the thin slurry of one deck earlier, dry the back and form carbon cloth with pasty film, this carbon cloth is placed on the suction filtration device shown in Figure 1, the first surface that does not wherein have the carbon cloth of pasty film contacts with the suction filtration device, the size of carbon cloth is big or small consistent with the suction filtration device, the bottom of suction filtration device is connected with bottle,suction by rubber stopper, the suction filtration bottle neck is connected with circulating water pump, then slurry is poured on the carbon cloth, open water pump simultaneously and slowly carry out suction filtration, pressure in the bottle,suction is 0.98 MPa, slurry in the process of suction filtration attached to carbon cloth on, drain and form thickness behind the solvent and be 100 microns and have the thin layer of a lot of micropores.The carbon cloth that will have thin layer then is put in 350 ℃ of stoves and is incubated 60 minutes, takes out after cooling, promptly gets gas diffusion layer for fuel cell.
The preparation of fuel cell electrode: with Pt/C catalyst (Pt content is 40 weight %): isopropyl alcohol: Nafion makes slurry with 17: 50: 10 mixing and stirring of weight ratio.Then slurry is coated on the above-mentioned gas diffusion layers that makes by spraying process, was positioned in 130 ℃ the baking oven baking after drying again 10 minutes in air, remove solvent, take out the cooling back.The content of Pt is 1 milligram/square centimeter in the fuel cell electrode.
The preparation of fuel cell membrane electrode: above-mentioned two electrodes that make are alignd with the both sides of proton exchange membrane Nafion115, and under 130 ℃ of temperature, under 2 MPa pressure, hot pressing 2 minutes forms the integrated film electrode.
Embodiment 5
Cathode preparation method and method for preparing membrane electrode that present embodiment is used to that the preparation method of gas diffusion layers provided by the invention is described and contains this gas diffusion layers.
The preparation of gas diffusion layers: with fuel cell with carbon cloth (6K Toray/127, toray company produce) 360 ℃ of sintering 60 minutes, be adsorbed on impurity in the carbon cloth with removal.Prepare the Kynoar emulsion of 30 weight % concentration, and then the carbon cloth behind the sintering put into wherein soak 2 times, soaked 5 minutes at every turn, take out then and dry.To be mixed into uniform slurry in conductive acetylene carbon black and the polyhexafluoropropylene adding ethylene glycol solvent, the content of polyhexafluoropropylene is that the weight of 20 weight %, conductive acetylene carbon black is 35 weight % in the slurry, and surplus is an ethylene glycol.On the second surface of carbon cloth, be coated with the thin slurry of one deck earlier, dry the back and form carbon cloth with pasty film, this carbon cloth is placed on the suction filtration device shown in Figure 1, the first surface that does not wherein have the carbon cloth of pasty film contacts with the suction filtration device, the size of carbon cloth is big or small consistent with the suction filtration device, the bottom of suction filtration device is connected with bottle,suction by rubber stopper, the suction filtration bottle neck is connected with circulating water pump, then slurry is poured on the carbon cloth, open water pump simultaneously and carry out suction filtration, pressure in the bottle,suction is 0.09 MPa, slurry in the process of suction filtration attached to carbon cloth on, drain and form thickness behind the solvent and be 110 microns and have the thin layer of a lot of micropores.The carbon cloth that will have thin layer then is put in 350 ℃ of stoves and is incubated 60 minutes, takes out after cooling, promptly gets the fuel battery negative pole gas diffusion layers.
The preparation of fuel cell membrane electrode: align in the both sides that above-mentioned two gas diffusion layers that make and two surfaces all had the proton exchange membrane Nafion117 (also being that marque is that the membrane electrode of GEFC-MEA4 is three-in-one) of Catalytic Layer, under 120 ℃ of temperature, under 5 MPa pressure, hot pressing 1 minute forms the integrated film electrode.The content of Pt is 1 milligram/square centimeter in the proton exchange membrane.
Embodiment 6
Cathode preparation method and method for preparing membrane electrode that present embodiment is used to that the preparation method of gas diffusion layers provided by the invention is described and contains this gas diffusion layers.
The preparation of gas diffusion layers: with fuel cell with carbon cloth (6K Toray/127, toray company produce) 400 ℃ of sintering 20 minutes, be adsorbed on impurity in the carbon cloth with removal.Prepare the poly-hexafluoroethylene emulsion of 10 weight % concentration, and then the carbon cloth behind the sintering put into wherein soak 7 times, soaked 6 minutes at every turn, take out then and dry, and insulation 30 minutes in 370 ℃ of stoves, be cooled to room temperature then.To be mixed into uniform slurry in VXC-72 carbon black and the Kynoar adding alcohol solvent, the content of Kynoar is that the content of 10 weight %, VXC-72 carbon black is 55 weight % in the slurry, and surplus is a solvent.On the second surface of carbon cloth, be coated with the thin slurry of one deck earlier, dry the back and form carbon cloth with pasty film, this carbon cloth is placed on the suction filtration device shown in Figure 1, the first surface that does not wherein have the carbon cloth of pasty film contacts with the suction filtration device, the size of carbon cloth is big or small consistent with the suction filtration device, the bottom of suction filtration device is connected with bottle,suction by rubber stopper, the suction filtration bottle neck is connected with circulating water pump, then slurry is poured on the carbon cloth, open water pump simultaneously and carry out suction filtration, the pressure of water pump is 0.02 MPa, slurry in the process of suction filtration attached to carbon cloth on, drain and form thickness behind the solvent and be 120 microns and have the thin layer of a lot of micropores.The carbon cloth that will have thin layer then is put in 310 ℃ of stoves and is incubated 70 minutes, takes out after cooling, promptly gets the fuel battery negative pole gas diffusion layers.
The preparation of fuel cell electrode: with Pt/C catalyst (Pt content is 20 weight %): isopropyl alcohol+glycerol (volume ratio 1: 1): Nafion makes slurry with 20: 49: 8 mixing and stirring of weight ratio.Then slurry is coated on the above-mentioned gas diffusion layers that makes by spraying process, was positioned in 120 ℃ the baking oven baking after drying again 30 minutes in air, so that remove solvent, take out the cooling back.The content of Pt is 1 milligram/square centimeter in the fuel cell electrode.
The preparation of fuel cell membrane electrode: above-mentioned two electrodes that make are alignd with the both sides of proton exchange membrane Nafion1035, and under 150 ℃ of temperature, under 0.5 MPa pressure, hot pressing 3 minutes forms the integrated film electrode.
Comparative example 1
Method according to embodiment 1 among the CN 1658422A prepares fuel battery gas diffusion layer, comprises the fuel cell electrode and the fuel cell membrane electrode of this diffusion layer.
Battery performance test
The battery that the foregoing description 1-6 and comparative example 1 make is tested with fuel battery test system (Fc Lab), the condition of test is: 60 ℃ of probe temperatures, 70 ℃ of hydrogen humidification temperature, hydrogen and air are normal pressure, and snake shape gas flowfield, catalytic activity area are 25 square centimeters.The current density of each battery in the time of 0.6 volt is as shown in table 1 below, wherein the battery performance figure of the battery that makes by embodiment 1,2 and comparative example 1 as shown in Figure 4, abscissa is that voltage (volt), ordinate are current density (milliampere/square centimeter).
Table 1
| The battery source | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Current density (milliampere/square centimeter) | 600 | 530 | 510 | 480 | 465 | 490 | 420 |
From the result of table 1 and Fig. 4 as can be seen, owing to adopt membrane electrode provided by the invention, thereby the high 10.7-42.9% of current density of the battery of the prior art that makes of the current density ratio comparative example 1 of fuel cell provided by the invention.Embodiment 2 is owing to use carbon paper without presintering, the current density of battery that made in the carbon paper contained impurity effect, and therefore the current density of the battery of the embodiment 1 more identical than other condition is low.
Claims (14)
1. the preparation method of a fuel battery gas diffusion layer, this method comprises that the slurry that will contain conductive agent and water-repelling agent is evenly distributed on the backing material, sintering contains the backing material of conductive agent and water-repelling agent then, it is characterized in that, first surface and second surface that the slurry that will contain conductive agent and water-repelling agent the method on the backing material of being evenly distributed to is included in backing material form pressure differential, the pressure of second surface is greater than the pressure of first surface, the slurry that will contain conductive agent and water-repelling agent contacts with the second surface of backing material, and first surface is respectively two relative surfaces of backing material with second surface.
2. method according to claim 1, wherein, the formation pressure difference method is the first surface one side suction filtration from backing material.
3. method according to claim 1, wherein, described pressure differential is the 0.01-0.1 MPa.
4. method according to claim 1, wherein, the consumption of described slurry makes conductive agent and water-repelling agent form the thin layer that thickness is the 50-200 micron on backing material.
5. method according to claim 1, wherein, the weight ratio of conductive agent and water-repelling agent is 1-10 in the described slurry: 1.
6. method according to claim 1, wherein, this method also is included in and forms before the pressure differential, earlier the part slurry is distributed on the second surface of backing material equably in advance.
7. method according to claim 1 wherein, before this method also is included in the slurry that will contain conductive agent and water-repelling agent and the second surface of backing material contacts, is soaked backing material earlier in water-repelling agent solution or emulsion.
8. method according to claim 7, wherein, the concentration of described water-repelling agent solution or emulsion is 5-30 weight %, the time of immersion is 10-70 minute.
9. method according to claim 1, wherein, before this method also is included in the slurry that will contain conductive agent and water-repelling agent and the second surface of backing material contacts, backing material is carried out presintering, the temperature of presintering is 340-400 ℃, and the time is 20-90 minute.
10. method according to claim 1, wherein, described backing material is a kind of in carbon paper, carbon cloth, the expanded metal, and described conductive agent is that carbon black and/or conductive acetylene are black, and described water-repelling agent is one or more in polytetrafluoroethylene, polyhexafluoropropylene, the Kynoar.
11. method according to claim 1, wherein, the condition that described sintering contains the backing material of conductive agent and water-repelling agent comprises that sintering temperature is 300-400 ℃, and sintering time is 5-100 minute.
12. the preparation method of a fuel cell electrode, this method are included in supported catalyst layer on the gas diffusion layers, wherein, described gas diffusion layers adopts any method preparation among the claim 1-11.
13. the preparation method of a fuel cell membrane electrode, this method comprise with two fuel cell electrodes respectively with two surface combination of proton exchange membrane, wherein, described fuel cell electrode adopts the described method preparation of claim 12.
14. the preparation method of a fuel cell membrane electrode, wherein, this method comprises two surface combination that two gas diffusion layers had the proton exchange membrane of Catalytic Layer respectively with the surface, and described gas diffusion layers adopts any described method preparation among the claim 1-11.
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| CN103165909B (en) * | 2011-12-19 | 2016-08-24 | 中国科学院大连化学物理研究所 | A kind of post-processing approach of fuel cell porous gas diffusion layer |
| JP5862485B2 (en) * | 2012-07-02 | 2016-02-16 | トヨタ自動車株式会社 | Method for forming gas diffusion layer for fuel cell |
| CN104064784A (en) * | 2013-03-20 | 2014-09-24 | 中国科学院大连化学物理研究所 | Method for improving stability of proton exchange membrane fuel cell |
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