CN101350412A - Gaseous diffusion layer for polymer electrolyte film fuel cell and preparation method thereof - Google Patents
Gaseous diffusion layer for polymer electrolyte film fuel cell and preparation method thereof Download PDFInfo
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- CN101350412A CN101350412A CNA2008101371319A CN200810137131A CN101350412A CN 101350412 A CN101350412 A CN 101350412A CN A2008101371319 A CNA2008101371319 A CN A2008101371319A CN 200810137131 A CN200810137131 A CN 200810137131A CN 101350412 A CN101350412 A CN 101350412A
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Abstract
The invention relates to a gaseous diffusion layer for a polymer electrolyte membrane fuel battery and a preparation method thereof, relating to a gaseous diffusion layer for a fuel battery and a preparation method thereof. The invention is capable of settling the problem of uneven distribution of carbon paper or hydrophobic material in the existing gaseous diffusion layer which degrades the performance of the fuel battery due to relatively big concentration polarization and ohm polarization of the gaseous diffusion layer. The porous-material layer in the gaseous diffusion layer comprises a porous fiber layer and carbon nano-palp growing on the fibers of the porous fiber layer. The preparation method of the invention includes the procedures that the porous fiber layer is rinsed and dried; nano-particles of cobalt, nickel or cobalt-nickel alloy are loaded onto the fiber surface; hydrophobic treatment is conducted; and the slurry is coated on the surface of the supporting layer and sintered. The hydrophobic materials of the gaseous diffusion layer are distributed evenly, as a result, the concentration polarization and the ohm polarization of the gaseous diffusion layer are lowered and the performance of the fuel battery is improved. Besides, the equipments needed by the method are simple and are easy to realize.
Description
Technical field
The present invention relates to a kind of gas diffusion layers that is used for fuel cell and preparation method thereof.
Background technology
Fuel cell is directly will be stored in the generation mode that chemical energy in fuel and the oxidant is converted into electric energy by electrochemical reaction, has outstanding advantages such as efficient height, environmental friendliness, is acknowledged as one of key technology that solves energy security and environmental pollution.Polymer dielectric film fuel cell have start fast, load response rapidly, distinct advantages such as miniaturization, use be flexible, have a extensive future in applications such as electric motor car, portable electric appts.Polymer dielectric film fuel cell mainly is made of assemblies such as dielectric film, Catalytic Layer, gas diffusion layers and flow-field plate.Gas diffusion layers is between flow-field plate and Catalytic Layer, its major function is a conduction electron between flow-field plate and Catalytic Layer, simultaneously with reacting gas by even flow field transfer to Catalytic Layer, and will react the water that generates and be transported to runner fast in order to avoid hinder the transmission of reacting gas.The quality of gas diffusion layers is very big to the overall performance impact of polymer dielectric film fuel cell.High performance gas diffusion layers must be made up of the porous material with satisfactory electrical conductivity, and porous material also will have extraordinary hydrophobicity simultaneously.
At present, the diffusion layer of polymer dielectric film fuel cell mainly is made up of supporting layer and microporous layers.Wherein supporting layer generally adopts the carbon paper or the carbon cloth of porous.Carbon paper and carbon cloth have good electrical conductivity, and porosity can be up to 90%, and can regulate within the specific limits, has good hydrophobicity in order to make carbon paper and carbon cloth, need carry out hydrophobic to carbon paper or carbon cloth and handle.The quality of hydrophobic treatment effect has very important influence to fuel battery performance.Carbon paper or carbon cloth are carried out the general impregnation sintering method that adopts of hydrophobic processing, be about in the emulsion of carbon paper or carbon cloth immersion polytetrafluoroethylene (PTFE) and perfluoroethylene third rare hydrophobic materials such as (FEP), take out dry back in 300 ℃～350 ℃ sintering, hydrophobic material then is coated on carbon paper or the carbon cloth fiber surface makes it obtain good hydrophobicity performance.But, there is tangible problem in this hydrophobic processing method, show that mainly hydrophobic materials such as PTFE and FEP can move the place of having a common boundary that is accumulated to less micropore of size and carbon fiber in dry and sintering process, making micropore and carbon fiber have a common boundary the place is filled by hydrophobic material, and the carbon fiber surface hydrophobic material at macropore place is less, causes hydrophobic material skewness in carbon paper or the carbon cloth.Because the micropore in carbon paper or the carbon cloth is the main passing away of product water, macropore then is the main transmission channel of gas, the hydrophobic material skewness not only can reduce the hydrophobicity of carbon paper or carbon cloth, the more important thing is that micropore can be caused the discharge difficulty of aqueous water and stop up macropore by the hydrophobic material filling, produce the water logging phenomenon, have a strong impact on the transmission of reacting gas and cause very big concentration polarization.Simultaneously, the contact resistance that carbon fiber is had a common boundary the place is one of main source of gas diffusion layers resistance, thereby the accumulation that hydrophobic material is had a common boundary the place at carbon fiber can influence the resistance that contact between carbon fiber can increase gas diffusion layers, produces bigger ohmic polarization.Be the performance that the concentration polarization or the increase of ohmic polarization all can reduce polymer dielectric film fuel cell, and the content of hydrophobic material is high more generally speaking, phenomenon pockety is obvious more, and its influence is serious more.
Summary of the invention
Thereby the gas diffusion layers that the objective of the invention is to be caused for hydrophobic material skewness in the carbon paper that solves existing gas diffusion layers or the carbon cloth exists big concentration polarization and ohmic polarization to reduce the problem of fuel cell performance, and then a kind of gas diffusion layers that is used for polymer dielectric film fuel cell and preparation method thereof is provided.
The gas diffusion layers that is used for polymer dielectric film fuel cell of the present invention is made up of supporting layer and microporous layers, described microporous layers covers on the surface of supporting layer, described supporting layer is made by the porous material layer of handling through hydrophobic, and described porous material layer is made up of porous fiber layer and the carbon nanowhisker on the fiber that is grown in porous fiber layer.
The preparation method who is used for the gas diffusion layers of polymer dielectric film fuel cell of the present invention finishes like this: a, with porous fiber layer at deionized water, ethanol or acetone soln with ultrasonic waves for cleaning 10～60 minutes, adopt the second distillation water washing to neutral after the taking-up again, under 40 ℃～100 ℃ temperature dry 1～3 hour then; B, at room temperature adopt electro-deposition, electronation or thermal reduction method nano particle, with this catalyst as the growth of carbon nanowhisker at fiber surface load cobalt, nickel or the cobalt-nickel alloy of porous fiber layer; C, porous fibre is placed in the tube furnace, the mist 1～30 minute that feeds methane, ethane, propane, ethene or above-mentioned gas under 500 ℃～1000 ℃ temperature in tube furnace is cooled to room temperature then naturally with growth carbon nanowhisker; D, porous fiber layer is immersed mass content is in 5～70% the hydrophobic material emulsion 1～15 minute, and it is dry in air or in the low-temperature bake oven to take out the back; E, repeating step d reach 10%～70% to porous fibrage weightening finish, then porous fiber layer are put into stove 200 ℃～400 ℃ sintering temperature 10～100 minutes, and layer is supported; F, with the emulsion of carbon black and hydrophobic material by siccative mass ratio 10: (1～15) is mixed and is prepared into slurry, made slurry is coated on the surface of supporting layer by spraying, blade coating or spread coating then, place stove heat treatment 10～100 minutes under 200 ℃～400 ℃ temperature then, promptly obtain the gas diffusion layers that will prepare.
The present invention compared with prior art has following beneficial effect: form coarse fiber surface by a large amount of carbon nanowhisker of growth on the fiber surface in porous fiber layer, can increase the interaction of fiber and hydrophobic material, suppress the accumulation of hydrophobic material in dry and sintering process, impel hydrophobic material in gas diffusion layers, evenly to distribute, this helps improving the hydrophobicity performance of gas diffusion layers, improve the mass transfer ability and the conductivity of gas diffusion layers, improve fuel cell performance.And the interaction of carbon nanowhisker and hydrophobic material can strengthen hydrophobic material and diffusion layer high base strength, improves the stability of gas diffusion layers hydrophobicity performance.And character such as the size by control carbon nanowhisker, stand density can change the distribution situation of hydrophobic material flexibly, thereby realize artificial design and regulation and control to the gas diffusion layers performance.The method applied in the present invention devices needed is simple in addition, realizes easily.
Description of drawings
Fig. 1 is the overall structure schematic diagram of gas diffusion layers of the present invention, the schematic diagram of the carbon nanowhisker of growing on the fiber surface of Fig. 2 porous material layer of the present invention, battery polarization curve chart in Fig. 3 specific embodiment of the invention 12, battery polarization curve chart in Fig. 4 specific embodiment of the invention 13, battery polarization curve chart in Fig. 5 specific embodiment of the invention 14, the battery polarization curve chart in Fig. 6 specific embodiment of the invention 15.
Embodiment
Embodiment one: present embodiment is described in conjunction with Fig. 1 and Fig. 2, the gas diffusion layers that is used for polymer dielectric film fuel cell of present embodiment is made up of supporting layer 1 and microporous layers 2, described microporous layers 2 covers on the surface of supporting layer 1, described supporting layer 1 is made by the porous material layer of handling through hydrophobic, and described porous material layer is made up of porous fiber layer and the carbon nanowhisker 4 on the fiber 3 that is grown in porous fiber layer.
Embodiment two: in conjunction with Fig. 2 present embodiment is described, the difference of present embodiment and embodiment one is: the porous fiber layer of present embodiment is made by carbon paper, carbon cloth or metal web.So be provided with, hydrophobic material is more evenly distributed in gas diffusion layers.
Embodiment three: in conjunction with Fig. 2 present embodiment is described, the difference of present embodiment and embodiment one is: the porosity of the porous fiber layer of present embodiment is 20%～95%, and average pore size is greater than 1um.So be provided with, hydrophobic material is more evenly distributed in gas diffusion layers.
Embodiment four: in conjunction with Fig. 2 present embodiment is described, the difference of present embodiment and embodiment one is: the carbon nanowhisker 4 of present embodiment is carbon nano-fiber or carbon nano-tube.So be provided with, hydrophobic material is more evenly distributed in gas diffusion layers.
Embodiment five: in conjunction with Fig. 2 present embodiment is described, the difference of present embodiment and embodiment one is: the length of the carbon nanowhisker 4 of present embodiment is 1nm～10um, and average diameter is 5nm～200nm.
Embodiment six: the preparation method of the gas diffusion layers that is used for polymer dielectric film fuel cell of present embodiment finishes like this: a, with porous fiber layer at deionized water, ethanol or acetone soln with ultrasonic waves for cleaning 10～60 minutes, adopt the second distillation water washing to neutral after the taking-up again, under 40 ℃～100 ℃ temperature dry 1～3 hour then; B, at room temperature adopt electro-deposition, electronation or thermal reduction method nano particle, with this catalyst as 4 growths of carbon nanowhisker at fiber 3 area load cobalts, nickel or the cobalt-nickel alloy of porous fiber layer; C, porous fibre is placed in the tube furnace, the mist 1～30 minute that feeds methane, ethane, propane, ethene or above-mentioned gas under 500 ℃～1000 ℃ temperature in tube furnace is cooled to room temperature then naturally with growth carbon nanowhisker 4; D, porous fiber layer is immersed mass content is in 5～70% the hydrophobic material emulsion 1～15 minute, and it is dry in air or in the low-temperature bake oven to take out the back; E, repeating step d reach 10%～70% to porous fibrage weightening finish, then porous fiber layer are put into stove 200 ℃～400 ℃ sintering temperature 10～100 minutes, and layer 1 is supported; F, with the emulsion of carbon black and hydrophobic material by siccative mass ratio 10: (1～15) is mixed and is prepared into slurry, made slurry is coated on the surface of supporting layer 1 by spraying, blade coating or spread coating then, place stove heat treatment 10～100 minutes under 200 ℃～400 ℃ temperature then, promptly obtain the gas diffusion layers that will prepare.
Embodiment seven: the difference of present embodiment and embodiment six is: present embodiment electro-deposition method described in the b step in the nitrate of sulfate, cobalt and the nickel of cobalt sulfate, cobalt nitrate, cobalt chloride, nickel sulfate, nickel nitrate, nickel chloride, cobalt and the nickel of 10mM～5M or chloride solution with the mode of direct current, pulse or cyclic voltammetric nano particle at fiber surface load cobalt, nickel or the cobalt-nickel alloy of porous fiber layer.The hydrophobicity performance of gas diffusion layers is better.
Embodiment eight: the difference of present embodiment and embodiment six is: present embodiment at chemical reduction method described in the b step in the nitrate of sulfate, cobalt and the nickel of cobalt sulfate, cobalt nitrate, cobalt chloride, nickel sulfate, nickel nitrate, nickel chloride, cobalt and the nickel of 10mM～5M or chloride solution, adding sodium borohydride, formaldehyde or reduction of ethylene glycol agent nano particle at fiber surface load cobalt, nickel or the cobalt-nickel alloy of porous fiber layer.The hydrophobicity performance of gas diffusion layers is better.
Embodiment nine: the difference of present embodiment and embodiment six is: present embodiment is heat-treated under 150 ℃～1000 ℃ temperature with reducibility gas hydrogen or carbon monoxide for soak 0.5～50 hour in the nitrate of sulfate, cobalt and the nickel of cobalt sulfate, cobalt nitrate, cobalt chloride, nickel sulfate, nickel nitrate, nickel chloride, cobalt and the nickel of 10mM～5M or chloride solution after in thermal reduction method described in the b step, at the nano particle of fiber surface load cobalt, nickel or the cobalt-nickel alloy of porous fiber layer.The hydrophobicity performance of gas diffusion layers is better.
Embodiment ten: the difference of present embodiment and embodiment six is: present embodiment is 1nm～150nm at the particle diameter of the nano particle of cobalt described in the b step, nickel or cobalt-nickel alloy.The hydrophobicity performance of gas diffusion layers is better.
Embodiment 11: the difference of present embodiment and embodiment six is: present embodiment is at hydrophobic material described in the d step that polytetrafluoroethylene, perfluoroethylene are third rare, copolymer, the polytrifluorochloroethylene of copolymer, tetrafluoroethene and the hexafluoropropylene of Kynoar, tetrafluoroethene and ethene or contain the fluoroalkyl oxosilane.The hydrophobicity performance of gas diffusion layers is better.
Embodiment 12: present embodiment is described in conjunction with Fig. 3, the difference of present embodiment and embodiment six is: present embodiment is in a step, choosing carbon paper (Toray TGPH 090) is porous fiber layer, under the room temperature carbon paper is used ultrasonic waves for cleaning 30 minutes in ethanol, to neutral, drying is 3 hours under 60 ℃ of temperature with the second distillation water washing in the taking-up back; In the b step, (plating bath is formed: nickelous sulfate 26g/L at nickelous sulfate plating liquid under the room temperature, boric acid 3.5g/L, lauryl sodium sulfate 0.01g/L, pH value 3.8) be anode with the nickel plate in, the carbon paper that cleaned is a negative electrode, and (sedimentary condition is: apparent current density is 20Am to the method for employing pulse electrodeposition at the surface deposition nano nickle granules of carbon paper fiber
-2, ON time is 10 milliseconds, dwell time is 200 milliseconds, electrodeposition time is 5 minutes), the carbon paper taking-up is extremely neutral with the second distillation water washing, and drying is 3 hours under 60 ℃ of temperature; In the c step, the carbon paper that deposited nano nickle granules is placed the mist of tube furnace logical argon gas and propane under 800 ℃ of temperature, and (propane content is 3%, and the mist total flow is 200ml min
-1) 10 minutes with growth carbon nanowhisker.Naturally after the cooling, that carbon paper is extremely neutral with the second distillation water washing, drying is 3 hours under 60 ℃ of temperature, the carbon nanowhisker of growing on the carbon paper fiber surface; In the d step, growth there is the carbon paper of carbon nanowhisker in 20% PTFE emulsion, soaked 2 minutes, take out the back and in air, dry; In the e step, repeating step d three times puts into carbon paper Muffle furnace then and handled 30 minutes under 340 ℃ of temperature; In the f step, take by weighing conductive carbon black (Vulcan XC-72, Cabot Co.) 0.5g and 40% PTFE emulsion 10g, both mix 30 minutes form slurry of the ultrasonic dispersion in back, and slurry is sprayed to above-mentioned carbon paper surface of handling through hydrophobic, and (carrying capacity of carbon black is 0.5mg cm
-2), will put into Muffle furnace through the carbon paper of this processing and under 340 ℃ of temperature, handle 30 minutes, promptly make gas diffusion layers.
With prepared gas diffusion layers and CCM membrane electrode (electrode area 1.5cm
2, dielectric film is the Nafion112 film, the platinum carrying capacity of Pt/C catalyst is 0.5mg cm
-2) be assembled into battery, carry out electrochemical property test.Test condition is: 25 ℃ of battery temperatures, and the hydrogen humidification temperature is 35 ℃, and air is humidification not, and hydrogen and air velocity are 100ml min
-1, obtain the discharge performance curve of battery.Fuel cell performance is improved.
Embodiment 13: present embodiment is described in conjunction with Fig. 4, the difference of present embodiment and embodiment six is: present embodiment is in a step, choosing carbon paper (Toray TGPH 090) is porous fiber layer, under the room temperature carbon paper is used ultrasonic waves for cleaning 30 minutes in ethanol, to neutral, drying is 3 hours under 60 ℃ of temperature with the second distillation water washing in the taking-up back; In the b step, in the nickel sulfate solution of 0.1M, be auxiliary electrode under the room temperature with the platinized platinum, the Ag/AgCl electrode is a reference electrode, the carbon paper that cleaned is a work electrode, the method that adopts cyclic voltammetric is at carbon paper fiber surface depositing nano nickel particle (scanning potential range: 0～1V, sweep speed 10mV s
-1, scanning times is 100 times), the carbon paper taking-up is extremely neutral with the second distillation water washing, and drying is 3 hours under 60 ℃ of temperature; In the c step, the carbon paper that deposited nano nickle granules is placed the mixed gas of tube furnace logical argon gas and hydrogen under 800 ℃ of temperature, and (hydrogen content is 5%, and mixed total gas flow rate is 200ml min
-1) after 10 minutes, (propane content is 3% to the mist of logical argon gas and propane in the mist, and the mist total flow is 200ml min
-1) 10 minutes with growth carbon nanowhisker, naturally after the cooling, with carbon paper with the second distillation water washing to neutral, drying is 3 hours under 60 ℃ of temperature; In the d step, growth there is the carbon paper of carbon nanowhisker in 20% PTFE emulsion, soaked 2 minutes, take out the back and in air, dry; In the e step, repeating step d three times puts into carbon paper Muffle furnace then and handled 30 minutes under 340 ℃ of temperature; In step f, take by weighing conductive carbon black (Vulcan XC-72, Cabot Co.) 0.5g and 40% PTFE emulsion 10g, both mix 30 minutes form slurry of the ultrasonic dispersion in back, and slurry is sprayed to above-mentioned carbon paper surface of handling through hydrophobic, and (carrying capacity of carbon black is 0.5mg cm
-2), will put into Muffle furnace through the carbon paper of this processing and under 340 ℃ of temperature, handle 30 minutes, promptly make gas diffusion layers.
With prepared gas diffusion layers and CCM membrane electrode (electrode area 1.5cm
2, dielectric film is the Nafion112 film, the platinum carrying capacity of Pt/C catalyst is 0.5mg cm
-2) be assembled into battery, carry out electrochemical property test.Test condition is: 25 ℃ of battery temperatures, and the hydrogen humidification temperature is 35 ℃, and air is humidification not, and hydrogen and air velocity are 100ml min
-1, obtain the discharge performance curve of battery.Fuel cell performance is improved.
Embodiment 14: present embodiment is described in conjunction with Fig. 5, the difference of present embodiment and embodiment six is: present embodiment is in a step, choosing carbon paper (Toray TGPH 090) is porous fiber layer, under the room temperature carbon paper is used ultrasonic waves for cleaning 30 minutes in acetone, to neutral, drying is 3 hours under 60 ℃ of temperature with the second distillation water washing in the taking-up back; In the b step, it is the ethanolic solution that the p-aminobenzoic acid of 50mM adds the lithium perchlorate of 100mM that the carbon paper that cleaned is put into concentration, with the platinized platinum is auxiliary electrode, the Ag/AgCl electrode is a reference electrode, the carbon paper that cleaned is a work electrode, under the room temperature in 0～1.0V potential range the speed of sweeping with 10mV/s carry out cyclic voltammetry scan 100 times, carbon paper is taken out with the second distillation water washing to neutral, drying is 3 hours under 60 ℃ of temperature, place the cobalt sulfate solution of 0.1M to soak 24 hours above-mentioned carbon paper, take out and use the second distillation water washing to neutral, drying is 3 hours under 60 ℃ of temperature; In the c step, carbon paper is placed the mixed gas of tube furnace logical argon gas and hydrogen under 800 ℃ of temperature, and (the mist hydrogen content is 5%, and the mist total flow is 200mlmin
-1) 10 minutes carry out thermal reduction after, (propane content is 3% to the mist of logical argon gas and propane in the mist, and mixed total gas flow rate is 200ml min
-1) 10 minutes with growth carbon nanowhisker, naturally after the cooling, with carbon paper with the second distillation water washing to neutral, drying is 3 hours under 60 ℃ of temperature; In the d step, growth there is the carbon paper of carbon nanowhisker in 20% PTFE emulsion, soaked 2 minutes, take out the back and in air, dry; In the e step, step e is three times repeatedly, then carbon paper is put into Muffle furnace and is handled 30 minutes under 340 ℃ of temperature; In the f step, (both mix 30 minutes form slurry of the ultrasonic dispersion in back for Vulcan XC-72, CabotCo.) 0.5g and 40% PTFE emulsion 10g, and slurry is sprayed to the carbon paper surface, and (carrying capacity of carbon black is 0.5mg cm to take by weighing conductive carbon black
-2), again carbon paper is put into Muffle furnace and under 340 ℃ of temperature, handled 30 minutes, promptly make gas diffusion layers.
With prepared gas diffusion layers and CCM membrane electrode (electrode area 1.5cm
2, dielectric film is the Nafion112 film, the platinum carrying capacity of Pt/C catalyst is 0.5mg cm
-2) be assembled into battery, carry out electrochemical property test.Test condition is: 25 ℃ of battery temperatures, and the hydrogen humidification temperature is 35 ℃, and air is humidification not, and hydrogen and air velocity are 100ml min
-1, obtain the discharge performance curve of battery.Fuel cell performance is improved.
Embodiment 15: present embodiment is described in conjunction with Fig. 6, the difference of present embodiment and embodiment six is: present embodiment is in a step, choose carbon cloth (E-TEK, Type A) is porous fiber layer, under the room temperature with carbon cloth under the room temperature in acetone with ultrasonic waves for cleaning 30 minutes, to neutral, drying is 3 hours under 60 ℃ of temperature with the second distillation water washing in the taking-up back; In the b step, in the cobalt nitrate solution of 0.1M, be auxiliary electrode under the room temperature with the platinized platinum, the Ag/AgCl electrode is a reference electrode, the carbon cloth that cleaned is a work electrode, the method that adopts cyclic voltammetric is at carbon cloth fiber surface depositing nano nickel particle (scanning potential range: 0～1V, sweep speed 10mV s
-1, scanning times is 100 times), the carbon cloth taking-up is extremely neutral with the second distillation water washing, and drying is 3 hours under 60 ℃ of temperature; In the c step, the carbon cloth that deposited nano nickle granules is placed the mixed gas of tube furnace logical argon gas and hydrogen under 800 ℃ of temperature, and (hydrogen content is 5%, and mixed total gas flow rate is 200ml min
-1) after 10 minutes, (propane content is 3% to the mist of logical argon gas and propane in the mist, and mixed total gas flow rate is 200mlmin
-1) 10 minutes with growth carbon nanowhisker, naturally after the cooling, with carbon cloth with the second distillation water washing to neutral, drying is 3 hours under 60 ℃ of temperature; In the d step, growth there is the carbon cloth of carbon nanowhisker in 20% PTFE emulsion, soaked 2 minutes, take out the back and in air, dry; In the e step, repeating step d three times puts into carbon cloth Muffle furnace then and handled 30 minutes under 340 ℃ of temperature; In the f step, take by weighing conductive carbon black (Vulcan XC-72, Cabot Co.) 0.5g and 40% PTFE emulsion 10g, both mix 30 minutes form slurry of the ultrasonic dispersion in back, and slurry is sprayed to above-mentioned carbon cloth surface of handling through hydrophobic, and (carrying capacity of carbon black is 0.5mg cm
-2), carbon cloth is put into Muffle furnace under 340 ℃ of temperature, handled 30 minutes, promptly make gas diffusion layers.
With prepared gas diffusion layers and CCM membrane electrode (electrode area 1.5cm
2, dielectric film is the Nafion112 film, the platinum carrying capacity of Pt/C catalyst is 0.5mg cm
-2) be assembled into battery, carry out electrochemical property test.Test condition is: 25 ℃ of battery temperatures, and the hydrogen humidification temperature is 35 ℃, and air is humidification not, and hydrogen and air velocity are 100ml min
-1, obtain the discharge performance curve of battery.Fuel cell performance is improved.
Embodiment 16: the difference of present embodiment and embodiment six is: present embodiment is in a step, choose carbon cloth (E-TEK, Type A) is porous fiber layer, under the room temperature carbon cloth is used ultrasonic waves for cleaning 30 minutes in acetone, to neutral, drying is 3 hours under 60 ℃ of temperature with the second distillation water washing in the taking-up back; In the b step, under 60 ℃ of temperature, the nickel nitrate solution of the carbon cloth that cleaned being put into 0.1M carries out the sonic oscillation stirring, saturated sodium borohydride solution is added drop-wise in the nickel nitrate solution gradually with reduced nickel ion (mole of sodium borohydride will surpass nickel ion reduce fully more than 3 times of required sodium borohydride amount), the carbon cloth taking-up is extremely neutral with the second distillation water washing, and drying is 3 hours under 60 ℃ of temperature; In the c step, the carbon cloth that deposited nano nickle granules is placed the mixed gas of tube furnace logical argon gas and hydrogen under 800 ℃ of temperature, and (hydrogen content is 5%, and mixed total gas flow rate is 200ml min
-1) after 10 minutes, (content of propane is 3% to the mist of logical argon gas and propane in the mist, and mixed total gas flow rate is 200ml min
-1) 10 minutes with growth carbon nanowhisker, naturally after the cooling, with carbon cloth with the second distillation water washing to neutral, drying is 3 hours under 60 ℃ of temperature; In the d step, growth there is the carbon cloth of carbon nanowhisker in 20% PTFE emulsion, soaked 2 minutes, take out the back and in air, dry; In the e step, repeating step d three times puts into carbon cloth Muffle furnace then in 340 ℃ of Temperature Treatment 30 minutes; In the f step, take by weighing conductive carbon black (Vulcan XC-72, Cabot Co.) 0.5g and 40% PTFE emulsion 10g, both mix 30 minutes form slurry of the ultrasonic dispersion in back, and slurry is sprayed to above-mentioned carbon cloth surface of handling through hydrophobic, and (carrying capacity of carbon black is 0.5mg cm
-2), again carbon cloth is put into Muffle furnace and under 340 ℃ of temperature, handled 30 minutes, promptly make gas diffusion layers.
Claims (10)
1, a kind of gas diffusion layers that is used for polymer dielectric film fuel cell, it is made up of supporting layer (1) and microporous layers (2), described microporous layers (2) covers on the surface of supporting layer (1), described supporting layer (1) is made by the porous material layer of handling through hydrophobic, it is characterized in that: described porous material layer is made up of porous fiber layer and the carbon nanowhisker (4) on the fiber (3) that is grown in porous fiber layer.
2, according to the described gas diffusion layers that is used for polymer dielectric film fuel cell of claim 1, it is characterized in that: described porous fiber layer is made by carbon paper, carbon cloth or metallic fiber net materials.
3, according to the described gas diffusion layers that is used for polymer dielectric film fuel cell of claim 1, it is characterized in that: the porosity of described porous fiber layer is 20%～95%, and average pore size is greater than 1um.
4, according to the described gas diffusion layers that is used for polymer dielectric film fuel cell of claim 1, it is characterized in that: described carbon nanowhisker (4) is carbon nano-fiber or carbon nano-tube, the length of described carbon nanowhisker 4 is 1nm～10um, and average diameter is 5nm～200nm.
5, a kind of preparation method who is used for the gas diffusion layers of polymer dielectric film fuel cell, the step that it is characterized in that described method is: a, with porous fiber layer in deionized water, ethanol or acetone soln with ultrasonic waves for cleaning 10～60 minutes, adopt the second distillation water washing to neutral after the taking-up again, under 40 ℃～100 ℃ temperature dry 1～3 hour then; B, at room temperature adopt electro-deposition, electronation or thermal reduction method nano particle, with this catalyst as carbon nanowhisker (4) growth at fiber (3) area load cobalt, nickel or the cobalt-nickel alloy of porous fiber layer; C, porous fibre is placed in the tube furnace, the mist 1～30 minute that feeds methane, ethane, propane, ethene or above-mentioned gas under 500 ℃～1000 ℃ temperature in tube furnace is cooled to room temperature then naturally with growth carbon nanowhisker (4); D, porous fiber layer is immersed mass content is in 5～70% the hydrophobic material emulsion 1～15 minute, and it is dry in air or in the low-temperature bake oven to take out the back; E, repeating step d reach 10%～70% to porous fibrage weightening finish, then porous fiber layer are put into stove 200 ℃～400 ℃ sintering temperature 10～100 minutes, and layer 1 is supported; F, with the emulsion of carbon black and hydrophobic material by siccative mass ratio 10: (1～15) is mixed and is prepared into slurry, made slurry is coated on the surface of supporting layer (1) by spraying, blade coating or spread coating then, place stove heat treatment 10～100 minutes under 200 ℃～400 ℃ temperature then, promptly obtain the gas diffusion layers that will prepare.
6, according to the described preparation method who is used for the gas diffusion layers of polymer dielectric film fuel cell of claim 5, it is characterized in that: electro-deposition method described in the b step in the nitrate of sulfate, cobalt and the nickel of cobalt sulfate, cobalt nitrate, cobalt chloride, nickel sulfate, nickel nitrate, nickel chloride, cobalt and the nickel of 10mM～5M or chloride solution with the mode of direct current, pulse or cyclic voltammetric nano particle at fiber surface load cobalt, nickel or the cobalt-nickel alloy of porous fiber layer.
7, according to the described preparation method who is used for the gas diffusion layers of polymer dielectric film fuel cell of claim 5, it is characterized in that: at chemical reduction method described in the b step in the nitrate of sulfate, cobalt and the nickel of cobalt sulfate, cobalt nitrate, cobalt chloride, nickel sulfate, nickel nitrate, nickel chloride, cobalt and the nickel of 10mM～5M or chloride solution, adding sodium borohydride, formaldehyde or reduction of ethylene glycol agent nano particle at fiber surface load cobalt, nickel or the cobalt-nickel alloy of porous fiber layer.
8, according to the described preparation method who is used for the gas diffusion layers of polymer dielectric film fuel cell of claim 5, it is characterized in that: be cobalt sulfate at 10mM～5M in thermal reduction method described in the b step, cobalt nitrate, the cobalt chloride, nickel sulfate, nickel nitrate, the nickel chloride, the sulfate of cobalt and nickel, soak in the nitrate of cobalt and nickel or the chloride solution after 0.5～50 hour and under 150 ℃～1000 ℃ temperature, heat-treat, at the fiber surface load cobalt of porous fiber layer with reducibility gas hydrogen or carbon monoxide, the nano particle of nickel or cobalt-nickel alloy.
9, according to claim 5,6, the 7 or 8 described preparation methods that are used for the gas diffusion layers of polymer dielectric film fuel cell, it is characterized in that: the particle diameter at the nano particle of cobalt described in the b step, nickel or cobalt-nickel alloy is 1nm～150nm.
10, according to the described preparation method who is used for the gas diffusion layers of polymer dielectric film fuel cell of claim 5, it is characterized in that: be at hydrophobic material described in the d step that polytetrafluoroethylene, perfluoroethylene are third rare, copolymer, the polytrifluorochloroethylene of copolymer, tetrafluoroethene and the hexafluoropropylene of Kynoar, tetrafluoroethene and ethene or contain the fluoroalkyl oxosilane.
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| CN104204302A (en) * | 2012-03-28 | 2014-12-10 | 贝卡尔特公司 | Assembly of a porous metal diffusion substrate and a polymeric separator membrane |
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| CN109334152A (en) * | 2018-10-08 | 2019-02-15 | 深圳市净万嘉环保科技有限公司 | High-temperature filter cloth and preparation method thereof |
| CN109334152B (en) * | 2018-10-08 | 2023-08-22 | 深圳市净万嘉环保科技有限公司 | High-temperature-resistant filter cloth and preparation method thereof |
| CN110783593A (en) * | 2019-10-22 | 2020-02-11 | 苏州然普能源有限公司 | Fuel cell gas diffusion layer and preparation method thereof |
| CN110783593B (en) * | 2019-10-22 | 2022-05-13 | 苏州然普能源有限公司 | Fuel cell gas diffusion layer and preparation method thereof |
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| CN111952601B (en) * | 2020-07-10 | 2022-08-16 | 华南理工大学 | Method for preparing integrated electrocatalytic oxygen evolution electrode through ultra-fast carbothermic reduction |
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