CN102082277B - Metal gas diffusion layer used for fuel cell and preparation method thereof - Google Patents
Metal gas diffusion layer used for fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a metal gas diffusion layer used for a fuel cell and a preparation method thereof. The preparation method comprises the following steps: preparing a stainless steel short fiber sintering felt by adopting a vacuum high temperature sintering method, then sequentially preparing a chromium layer and a graphite layer on the pretreated stainless steel short fiber sintering felt by adopting a closed field unbalanced magnetron sputtering ion plating technology, and then carrying out hydrophobic processing on the entire of the coated stainless steel short fiber sintering felt by utilizing polytetrafluoroethylene; and finally coating powdered carbon on the surface by adopting an ultrasonic oscillation method to obtain the metal gas diffusion layer used for the fuel cell. In the invention, stainless steel fiber with low price is taken as raw material, the high temperature vacuum sintering method is adopted to prepare the sintering felt, and the magnetron sputtering ion plating technology is utilized to prepare a carbon coating so as to improve the contact performance and anti-corrosion performance of the metal gas diffusion layer, thus the high-performance gas diffusion layer used for the fuel cell is prepared with low cost.
Description
Technical field
What the present invention relates to is material and the method in a kind of fuel cell technology field, specifically a kind of metal gas diffusion layer for fuel cell and preparation method thereof.
Background technology
Fuel cell is a kind of efficient, eco-friendly Blast Furnace Top Gas Recovery Turbine Unit (TRT), the chemical energy that it directly will be stored in fuel and oxidant is converted into electric energy, is subject to the great attention of national governments and research institution under the background of greatly developing low-carbon economy and construction low-carbon (LC) society.Proton Exchange Membrane Fuel Cells PEMFC has and starts soon, and working temperature is low, and noiseless and the advantage such as pollution-free have a wide range of applications in electric automobile, family expenses dwelling house, middle-size and small-size power station and mancarried device.Typical Proton Exchange Membrane Fuel Cells main body is bipolar plates, the repetition of membrane electrode assembly MEAs and corresponding seal unit, and outermost both sides are end plate.Membrane electrode assembly is prepared from by heat pressing process by gas diffusion layers, Catalytic Layer and proton exchange membrane usually.
Gas diffusion layers is comprised of the porous material of conductive and heat-conductive, plays the support Catalytic Layer, collected current and the effects such as conduction reacting gas and discharge water.Carbon fiber paper and carbon cloth have higher porosity and suitable pore-size distribution, have simultaneously heat conduction preferably, conductive characteristic and chemically stable, are the gas diffusion layer materials that is most widely used at present.Yet carbon fiber paper and carbon cloth are fragile material, easily cause the failure modes such as fibrous fracture, MATRIX CRACKING, fiber and basal body interface peel off in the situations such as assembling pressure, extraneous vibration and repeated disassembled and assembled, affect battery life.
Find through the retrieval to prior art, the people such as T.Matsuura [see T.Matsuura, M.Kato, M.Hori, J.Power Sources, 2006,161:74-78] adopt the method for scanning electron microscope sem to observe obvious failure behaviour in carbon paper type GDL and metal double polar plates assembling process.Simultaneously, carbon fiber type gas diffusion layers modulus of compressibility is less, causes larger compression under the assembling pressure effect, causes aperture and porosity to change, and causes resistance to mass tranfer to increase, and has improved the concentration polarization loss, has reduced fuel battery performance.The people such as P.Zhou [P.Zhou, C.W.Wu, J.Power Sources, 2007,170:93-100] adopt the method for finite element analysis to find to have reduced by 70% before under the bipolar plates ridge, gas concentration applies than assembling pressure after the assembling pressure effect, and serious seeping phenomenon appears, reduced battery performance.In addition, the carbon fiber type gas diffusion layers can not carry out bending, can't satisfy as Chinese patent ZL 97201080.7, and ZL 01126123.4, and ZL 03217133.1, the novel proton exchange membranes Structural Design Requirement that proposes in ZL 200710043435.4 grades.
Metal polyporous material has ductility and larger modulus of compressibility preferably, has simultaneously good heat conduction, conductive properties, is expected to replace carbon fibre material and becomes gas diffusion layers, improves battery mass-transfer performance and cell durability energy.Find through the retrieval to prior art, adopt the tinsel with minute aperture can improve drainage performance as gas diffusion layers.[see F.-Y.Zhang as people such as F.-Y.Zhang, S.G.Advani, A.K.Prasad, J.Power Sources, 176:293-298] adopt photoetching process to prepare the pore of 35 microns on 12.5 micron copper foils, the people such as K.Fushinobu [see K.Fushinobu, D.Takahashi, K.Okazaki, J.Power Sources, 158:1240-1245] adopt the method for microfabrication to process the aperture of 25 microns on the titanium foil of 10 microns, the people such as C.-Y.Lee [see C.-Y.Lee, C.-H.Lin, Renewable Energy, 35:759-762] aperture that adopts the MEMs technology to process 150 microns on the stainless steel paillon foil of 50 micron thickness makes the passage of reacting gas and water.Yet, adopt lowly as the gas diffusion layers working (machining) efficiency with the tinsel of minute aperture, processing cost is higher, can't satisfy the large-scale production requirement.The people such as T.Hottinen [T.Hottinen, M.Mikkola, T.Mennola, P.Lund, J.Power Sources 118 2003 183-188] thus adopt titanium sintering felt to improve film electrode structure intensity and durability as the PEMFC gas diffusion layers, by improving contact performance and Corrosion Protection in the method for titanium sintering felt plated surface Pt, improve battery performance.China Patent Publication No. is that CN 101140990A propose to adopt Pt, Au, the wire nettings such as Ru to support carbon dust and hydrophobic organic compound as gas diffusion layers, have solid firmly, can be made into the characteristics such as various shapes.Yet the noble metal costs such as Pt are higher, cause the manufacturing cost of fuel cell pile to rise, and can't satisfy the low-cost requirement of fuel cell large-scale application.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of metal gas diffusion layer for fuel cell and preparation method thereof is provided, and the large and less fracture failure that causes of modulus of compressibility and gas such as are difficult to enter at the problem due to fragility to solve traditional carbon fibres type gas diffusion layers.With cheap stainless steel fibre as raw material, adopt the method for high-temperature vacuum sintering to prepare the sintering felt, be aided with the magnetic controlled sputtering ion plating technology and prepare one deck carbon film, to increase its contact performance and Corrosion Protection, realize the high-performance and low-cost manufacturing of gas diffusion layer for fuel cell.
The present invention is achieved through the following technical solutions:
The present invention relates to a kind of metal gas diffusion layer for fuel cell, its thickness of diffusion layer is 0.15～0.25mm, and density is 1.2～2.5g/cm
3The metallic fiber diameter is 5～20 μ m, and pore diameter range is 5～50 μ m, and porosity is 70%～85%, and air permeability is 40～300L/mindm
2Thickness direction resistivity is about 50～80 μ Ω cm, and face direction thermal conductivity is about 15～21W/mK; Yield strength is more than 200MPa, and tensile strength is more than 400MPa; Corrosion current is lower than 1 * 10 under simulation Proton Exchange Membrane Fuel Cells operational environment
-6A/cm
2, under the contact effect of 1.5MPa with bipolar plate of stainless steel Contact resistance of the same race lower than 20m Ω/cm
2
The present invention relates to the preparation method of above-mentioned metal gas diffusion layer, method by vacuum high-temperature sintering prepares stainless steel short fiber sintering felt, then adopt the closed field unbalanced magnetron sputtering ion plating technique preparing successively chromium layer and graphite linings through on pretreated stainless steel short fiber sintering felt, adopting polytetrafluoroethylene to carry out hydrophobic to plated film stainless steel short fiber sintering felt integral body processes again, adopt at last ultrasonic concussion method to carry out surperficial powdered carbon and apply, obtain the metal gas diffusion layer for fuel cell.
Described vacuum high-temperature sintering refers to: be the synthetic bundle of stainless steel wire of 1～2mm with diameter, adopt the method for boundling drawing to obtain the stainless steel long-fiber bundle that diameter is 5～20 μ m, it is the short fiber bundle of 3～6mm that fiber beam cutting is become average length, then is placed on sintering under the vacuum environment of 1000 ℃～1200 ℃ through bulk processing.
Described bulk processing refers to: the short fiber bundle is placed in aqueous medium, adopts certain stirring intensity to become the ultimate fibre state to be prepared into uniform aaerosol solution the fibre bundle shredding with mixing speed.Under action of gravitation, the short fiber natural subsidence presents in a jumble arranges, and the moisture evaporation is namely obtained fluffy isotropic short fiber layers.
The thickness of described stainless steel short fiber sintering felt is 0.15～0.25mm, mutually intersects to form the space between the fiber in fiber sintering felt serving.
Described preliminary treatment refers to: adopt ultrasonic technology to carry out alkali cleaning, pickling, washed with de-ionized water process to stainless steel short fiber sintering felt, then dry the processing.
Described closed field unbalanced magnetron sputtering ion plating technique refers to: the argon gas of employing 99.99% purity and the helium of 99.99% purity are evacuated pressure lower than 3.0 * 10 as sputter gas with furnace chamber
-3Handkerchief, then remove the fiber passivation layer again with ar atmo bombardment stainless steel short fiber sintering felt, take the chromium of 99.99% purity as the plated surface one deck chromium layer of target at stainless steel short fiber sintering felt, then take the graphite of 99.99% purity as target in fibrofelt plated surface one deck graphite linings.
The thickness of described chromium layer is 0.2 μ m, and the thickness of described graphite linings is 1 μ m.
The fiber porosity of described plated film stainless steel short fiber sintering felt integral body is 70%～85%, and the aperture is between 5～50 μ m, and air permeability is 40L/mindm
2Above, thickness direction resistivity is about 50～80 μ Ω cm, and face direction thermal conductivity is about 15～21W/mK, and yield strength is more than 200MPa, and tensile strength is more than 400MPa.
Described hydrophobic is processed and is referred to: adopt the polytetrafluoroethylene emulsified material to soak plated film stainless steel short fiber sintering felt integral body by baking.
In described ptfe emulsion, the average grain diameter of polytetrafluoroethylene is 0.1～0.3 μ m.
The ultrasonic concussion method of described employing is carried out surperficial powdered carbon coating and referred to: the mixture of water or water and ethanol is as solvent, and powdered carbon mixes the surface that evenly is coated to afterwards the plated film stainless steel short fiber sintering felt of processing through hydrophobic by ultrasonic dispersion as solute with polytetrafluoroethylene.
Described powdered carbon adopts acetylene carbon black.
The present invention adopts the high-temperature vacuum sintering technology to prepare metallic fiber sintered felt, adopt the closed field unbalanced magnetron sputtering ion plating technique to prepare one deck anti-corrosion film, adopt PTFE to carry out hydrophobic treatment and adopt carbon dust to carry out smooth processing to prepare used in proton exchange membrane fuel cell metal gas diffusion layer.This gas diffusion layers has mechanical performance preferably, and large and the less fracture failure that causes of modulus of compressibility, gas such as are difficult to enter at the problem due to fragility to solve traditional carbon fibres type gas diffusion layers.Simultaneously, this gas diffusion layers fibre length, aperture and porosity are easily controlled, and are conducive to improve mass transfer characteristic under the operation of fuel cells operational environment.In addition, metal GDL overcomes the unyielding shortcoming of traditional GDL, can be processed into arbitrary shape, satisfies the Novel electric pile structure designing requirements such as wavy shaped configuration, for the fuel cell pile structure innovation provides possibility.At last, the metal gas diffusion layer Corrosion Protection of plated film significantly improves, and satisfies the challenge of fuel cell faintly acid operational environment, with the plating identical carbon film metal double polar plates Contact resistance seldom, reduce the ohmic loss of fuel cell kinetic potential, thereby promoted fuel battery performance.
Description of drawings
Fig. 1 is the curve chart that the plated film metal gas diffusion layer for preparing of the present invention and the contact resistance between the plated film metal double polar plates change with contact.
Fig. 2 is the corrosion current polarization curve of plated film metal gas diffusion layer under analog fuel cell cathode environment that the present invention prepares.
Fig. 3 is the monocell performance curve of the plated film metal gas diffusion layer assembling for preparing of the present invention.
Embodiment
The below elaborates to embodiments of the invention, and the present embodiment is implemented under take technical solution of the present invention as prerequisite, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
It is 5 μ m stainless steel fine fibre bundles that the stainless steel wire bundle drawing that the method that adopts the boundling drawing is 1mm with diameter obtains average diameter, it is the short fiber of 3mm that the segment of fine fibre bundle is become average length, short fiber is prepared the bulk felt of short fiber orientation random distribution through bulk processing.Bulk felt is put into vacuum furnace carry out high temperature sintering, sintering temperature is 1000 ℃, and obtaining thickness is the stainless steel fibre sintering felt of 0.15mm.
Cut stainless steel fibre sintering felt sample, carry out preliminary treatment: adopt the cleaning of 0.2M diluted sodium hydroxide solution repeatedly, remove surface organic matter, then with the washing of 0.6M dilution heat of sulfuric acid repeatedly, remove surface metal ion, then with the deionized water washing, dry.Above cleaning process all adopts ultrasonic cleaning technology.The sample that preliminary treatment is good is put into the closed field unbalanced magnetron sputtering ion plating equipment, equipment is vacuumized, the graphite of employing high-purity 99.99% and the chromium of high-purity 99.99% are as target, and high-purity 99.99% argon gas and high-purity 99.99% helium are as sputter gas.At first, adopt ar atmo bombardment fibrofelt, remove surface passivation layer, secondly at the ultra-thin chromium layer of fibrofelt plated surface one deck, last take chromium as target, take graphite as target at fibrofelt plated surface one deck graphite coating.After testing, ultra-thin chromium layer is 0.2 μ m, and graphite coating is 1 μ m.
The stainless steel fibre felt of plated film is first weighed, then repeatedly immerse concentration and be in 5% polytetrafluoroethylene emulsified material and soak, it is made hydrophobic process.It is roasting in the baking oven of 330 ℃～340 ℃ that the bipolar plates of having soaked PTFE is taken out the shady dried temperature that is placed on, the contained surfactant of ptfe emulsion that is immersed in fleece is removed, make simultaneously the PTFE hot melt sintering and be dispersed on fiber, thereby reach good hydrophobic effect, be built with the gas passage that is beneficial to gas transport.After roasting, fibrofelt is fully cooling and weigh, can determine the content of polytetrafluoroethylene in the metal gas diffusion layer, thereby determine the degree that hydrophobic is processed.Gas diffusion layers surface irregularity after oven dry, can affect the quality of catalyst layer, therefore, be necessary smooth processing is carried out on stainless steel fibre felt surface, its technique is: the mixed liquor of water and ethanol is as solvent, and it is the solution of 1: 1 that acetylene carbon black and PTFE are made into mass ratio, uses ultrasonic oscillation, it is mixed, then make its sedimentation.Remove top after the stillness of night, precipitum is applied on the stainless steel fibre sintering felt gas diffusion layers that carried out the hydrophobic processing, namely obtain flat surface after shady doing.
Adopting the stainless steel fibre sintering felt gas diffusion layers density of this example preparation is 2.19g/cm
3, pore diameter range is 5～20 μ m, porosity is 70%.Must this metal gas diffusion layer air permeability be 47L/mindm according to GB/T 1038-2000 standard testing
2, thickness direction resistivity is about 50 μ Ω cm, and face direction thermal conductivity is about 21W/mK, and yield strength is 250MPa, and tensile strength is 500MPa.As shown in Figure 1, adopt plated film metal gas diffusion layer that the electrochemical corrosion measuring instrument surveys under simulation Proton Exchange Membrane Fuel Cells operational environment corrosion current lower than 1 * 10
-8A/cm
2As shown in Figure 2, adopt the contact resistance test bed testing to obtain plated film stainless steel fibre felt and plated film bipolar plate of stainless steel Contact resistance is 6m Ω/cm at the contact of 1.5MPa
2Adopt the monocell power density of this metal gas diffusion layer assembling can reach 395mW/cm
2, as shown in Figure 3.Test condition: anode and cathode catalysis agent content: 0.3mg Pt/cm
-2, proton exchange membrane is Nafion117, and stack temperature is 80 ℃, and negative electrode, anode reaction temperature degree are 80 ℃, and humidity is 100%, pressure is 0.3MPa.
Embodiment 2
It is 10 μ m stainless steel fine fibre bundles that the stainless steel wire bundle drawing that the method that adopts the boundling drawing is 1mm with diameter obtains average diameter, and it is the short fiber of 4mm that the segment of fine fibre bundle is become average length, obtains the bulk felt of short fiber orientation random distribution through bulk processing.Bulk felt is put into vacuum furnace carry out high temperature sintering, sintering temperature is 1050 ℃, and obtaining thickness is the stainless steel fibre sintering felt of 0.17mm.
Cut stainless steel fibre sintering felt sample, carry out preliminary treatment: adopt the 0.4M diluted sodium hydroxide solution to clean repeatedly, remove surface organic matter, then with the washing of 1.0M dilution heat of sulfuric acid repeatedly, removing surface metal ion, with the deionized water washing, is to boil 30 minutes in 70 ℃ of concentration oxalic acid aqueous solution that is 5wt% in temperature, again with deionized water washing, oven dry.Above cleaning process all adopts ultrasonic cleaning technology.The sample that preliminary treatment is good is put into the closed field unbalanced magnetron sputtering ion plating equipment, equipment is vacuumized, the graphite of employing high-purity 99.99% and the chromium of high-purity 99.99% are as target, and high-purity 99.99% argon gas and high-purity 99.99% helium are as sputter gas.At first, adopt ar atmo bombardment fibrofelt, remove surface passivation layer, secondly at the chromium layer of fibrofelt plated surface a layer thickness as 0.2 μ m, last take chromium as target, be 1 μ m graphite coating take graphite as target in fibrofelt plated surface a layer thickness.
The stainless steel fibre felt of plated film is first weighed, then repeatedly immerse concentration and be in 5% polytetrafluoroethylene emulsified material and soak, it is made hydrophobic process.It is roasting in the baking oven of 330 ℃～340 ℃ that the bipolar plates of having soaked PTFE is taken out the shady dried temperature that is placed on, the contained surfactant of ptfe emulsion that is immersed in fleece is removed, make simultaneously the PTFE hot melt sintering and be dispersed on fiber, thereby reach good hydrophobic effect, be built with the gas passage that is beneficial to gas transport.After oven dry, smooth processing is carried out on stainless steel fibre felt surface, its technique is: the mixed liquor of water and ethanol is as solvent, and it is the solution of 1: 1 that acetylene carbon black and PTFE are made into mass ratio, uses ultrasonic oscillation, it is mixed, then make its sedimentation.Remove top after the stillness of night, precipitum is applied on the stainless steel fibre sintering felt gas diffusion layers that carried out the hydrophobic processing, namely obtain flat surface after shady doing.
Adopting the stainless steel fibre sintering felt gas diffusion layers density of this example preparation is 1.83g/cm
3, pore diameter range is 10～30 μ m, porosity is 75%.Must this metal gas diffusion layer air permeability be 105L/mindm according to GB/T 1038-2000 standard testing
2, thickness direction resistivity is about 61 μ Ω cm, and face direction thermal conductivity is about 19W/mK, and yield strength is 242MPa, and tensile strength is 480MPa.As Fig. 1, plated film metal gas diffusion layer under simulation Proton Exchange Membrane Fuel Cells operational environment corrosion current lower than 1 * 10
-8A/cm
2As Fig. 2, plated film stainless steel fibre felt and plated film bipolar plate of stainless steel Contact resistance are 6m Ω/cm at the contact of 1.5MPa
2Adopt the monocell power density of this metal gas diffusion layer assembling can reach 418mW/cm
2, as shown in Figure 3.Test condition: anode and cathode catalysis agent content: 0.3mg Pt/cm
-2, proton exchange membrane is Nafion117, and stack temperature is 80 ℃, and negative electrode, anode reaction temperature degree are 80 ℃, and humidity is 100%, pressure is 0.3MPa.
Embodiment 3
It is 12.5 μ m stainless steel fine fibre bundles that the stainless steel wire bundle drawing that the method that adopts the boundling drawing is 2mm with diameter obtains average diameter, it is the short fiber of 6mm that the segment of fine fibre bundle is become average length, short fiber is prepared the bulk felt of short fiber orientation random distribution through bulk processing.Bulk felt is put into vacuum furnace carry out high temperature sintering, sintering temperature is 1100 ℃, and obtaining thickness is the stainless steel fibre sintering felt of 0.19mm.
Cut stainless steel fibre sintering felt sample, carry out preliminary treatment: adopt the 1.0M diluted sodium hydroxide solution to clean repeatedly, remove surface organic matter, then with the washing of 1.0M dilution heat of sulfuric acid repeatedly,, remove surface metal ion, wash with deionized water, be to boil 30 minutes in 70 ℃ of concentration oxalic acid aqueous solution that is 10wt% in temperature, then with deionized water washing, oven dry.Above cleaning process all adopts ultrasonic cleaning technology.The sample that preliminary treatment is good is put into the closed field unbalanced magnetron sputtering ion plating equipment, equipment is vacuumized, the graphite of employing high-purity 99.99% and the chromium of high-purity 99.99% are as target, and high-purity 99.99% argon gas and high-purity 99.99% helium are as sputter gas.At first, adopt ar atmo bombardment fibrofelt, remove surface passivation layer, secondly at the ultra-thin chromium layer of fibrofelt plated surface one deck, last take chromium as target, take graphite as target at fibrofelt plated surface one deck graphite coating.After testing, ultra-thin chromium layer is 0.2 μ m, and graphite coating is 1 μ m.
The stainless steel fibre felt of plated film is first weighed, then repeatedly immerse concentration and be in 5% polytetrafluoroethylene emulsified material and soak, it is made hydrophobic process.It is roasting in the baking oven of 330 ℃～340 ℃ that the bipolar plates of having soaked PTFE is taken out the shady dried temperature that is placed on, the contained surfactant of ptfe emulsion that is immersed in fleece is removed, make simultaneously the PTFE hot melt sintering and be dispersed on fiber, thereby reach good hydrophobic effect, be built with the gas passage that is beneficial to gas transport.After roasting, fibrofelt is fully cooling and weigh, can determine the content of polytetrafluoroethylene in the metal gas diffusion layer, thereby determine the degree that hydrophobic is processed.Gas diffusion layers surface irregularity after oven dry, can affect the quality of catalyst layer, therefore, be necessary smooth processing is carried out on stainless steel fibre felt surface, its technique is: the mixed liquor of water and ethanol is as solvent, and it is the solution of 1: 1 that acetylene carbon black and PTFE are made into mass ratio, uses ultrasonic oscillation, it is mixed, then make its sedimentation.Remove top after the stillness of night, precipitum is applied on the stainless steel fibre sintering felt gas diffusion layers that carried out the hydrophobic processing, namely obtain flat surface after shady doing.
Adopting the stainless steel fibre sintering felt gas diffusion layers density of this example preparation is 1.54g/cm
3, porosity is 79%.Must this metal gas diffusion layer air permeability be 205L/mindm according to GB/T 1038-2000 standard testing
2, thickness direction resistivity is about 72 μ Ω cm, and face direction thermal conductivity is about 17W/mK, and adopting universal testing machine to record this stainless steel fibre sintering felt yield strength is 229MPa, and tensile strength is 450MPa.As shown in Figure 1, adopt plated film metal gas diffusion layer that the electrochemical corrosion measuring instrument surveys under simulation Proton Exchange Membrane Fuel Cells operational environment corrosion current lower than 1 * 10
-8A/cm
2As shown in Figure 2, adopt the contact resistance test bed testing to obtain plated film stainless steel fibre felt and plated film bipolar plate of stainless steel Contact resistance is 6m Ω/cm at the contact of 1.5MPa
2Adopting this metal gas diffusion layer and proton exchange membrane is Nafion117 hot pressing MEA, and the monocell power density of assembling can reach 450mW/cm
2, as shown in Figure 3.Test condition: anode and cathode catalysis agent content: 0.3mg Pt/cm
-2, stack temperature is 80 ℃, and negative electrode, anode reaction temperature degree are 80 ℃, and humidity is 100%, and pressure is 0.3Mpa.
Embodiment 4
It is 20 μ m stainless steel fine fibre bundles that the stainless steel wire bundle drawing that the method that adopts the boundling drawing is 2mm with diameter obtains average diameter, and it is the short fiber of 5mm that the segment of fine fibre bundle is become average length, obtains the bulk felt of short fiber orientation random distribution through bulk processing.Bulk felt is put into vacuum furnace carry out high temperature sintering, sintering temperature is 1200 ℃, and obtaining thickness is the stainless steel fibre sintering felt of 0.24mm.
Cut stainless steel fibre sintering felt sample, carry out preliminary treatment: adopt the cleaning of 0.8M diluted sodium hydroxide solution repeatedly, remove surface organic matter, then with the washing of 0.8M dilution heat of sulfuric acid repeatedly, remove surface metal ion, then with the deionized water washing, dry.Above cleaning process all adopts ultrasonic cleaning technology.The sample that preliminary treatment is good is put into the closed field unbalanced magnetron sputtering ion plating equipment, equipment is vacuumized, the graphite of employing high-purity 99.99% and the chromium of high-purity 99.99% are as target, and high-purity 99.99% argon gas and high-purity 99.99% helium are as sputter gas.At first, adopt ar atmo bombardment fibrofelt, remove surface passivation layer, secondly at the chromium layer of fibrofelt plated surface a layer thickness as 0.2 μ m, last take chromium as target, be 1 μ m graphite coating take graphite as target in fibrofelt plated surface a layer thickness.
The stainless steel fibre felt of plated film is first weighed, then repeatedly immerse concentration and be in 5% polytetrafluoroethylene emulsified material and soak, it is made hydrophobic process.It is roasting in the baking oven of 330 ℃～340 ℃ that the bipolar plates of having soaked PTFE is taken out the shady dried temperature that is placed on, the contained surfactant of ptfe emulsion that is immersed in fleece is removed, make simultaneously the PTFE hot melt sintering and be dispersed on fiber, thereby reach good hydrophobic effect, be built with the gas passage that is beneficial to gas transport.After oven dry, smooth processing is carried out on stainless steel fibre felt surface, its technique is: the mixed liquor of water and ethanol is as solvent, and it is the solution of 2: 1 that acetylene carbon black and PTFE are made into mass ratio, uses ultrasonic oscillation, it is mixed, then make its sedimentation.Remove top after the stillness of night, precipitum is applied on the stainless steel fibre sintering felt gas diffusion layers that carried out the hydrophobic processing, namely obtain flat surface after shady doing.
Adopting the stainless steel fibre sintering felt gas diffusion layers density of this example preparation is 1.47g/cm
3, pore size is 30～50 μ m, porosity is 80%.This metal gas diffusion layer air permeability is 280L/mindm
2, thickness direction resistivity is about 80 μ Ω cm, and face direction thermal conductivity is about 15W/mK, and yield strength is 200MPa, and tensile strength is 400MPa.As shown in Figure 1, adopt plated film metal gas diffusion layer that the electrochemical corrosion measuring instrument surveys under simulation Proton Exchange Membrane Fuel Cells operational environment corrosion current lower than 1 * 10
-8A/cm
2As shown in Figure 2, adopt the contact resistance test bed testing to obtain plated film stainless steel fibre felt and plated film bipolar plate of stainless steel Contact resistance is 6m Ω/cm at the contact of 1.5MPa
2Adopting this metal gas diffusion layer and proton exchange membrane is Nafion117 hot pressing MEA, and the monocell power density of assembling can reach 402mW/cm
2, as shown in Figure 3.Test condition: anode and cathode catalysis agent content: 0.3mg Pt/cm
-2, stack temperature is 80 ℃, and negative electrode, anode reaction temperature degree are 80 ℃, and humidity is 100%, and pressure is 0.3MPa.
Compare and can get with embodiment 1,2,4, technological parameter used in example 3 can obtain the optimum fuel battery performance.Therefore, fibre diameter is 12.5 μ m, and gas diffusion layers thickness is 0.19mm, and the aperture is 15～40 μ m, and porosity is 79%.
Claims (7)
1. preparation method who is used for the metal gas diffusion layer of fuel cell, it is characterized in that, method by vacuum high-temperature sintering prepares stainless steel short fiber sintering felt, then adopt the closed field unbalanced magnetron sputtering ion plating technique preparing successively chromium layer and graphite linings through on pretreated stainless steel short fiber sintering felt, adopting polytetrafluoroethylene to carry out hydrophobic to plated film stainless steel short fiber sintering felt integral body processes again, adopt at last ultrasonic concussion method to carry out surperficial powdered carbon and apply, obtain the metal gas diffusion layer for fuel cell;
Described vacuum high-temperature sintering refers to: be the synthetic bundle of stainless steel wire of 1～2mm with diameter, adopt the method for boundling drawing to obtain the stainless steel long-fiber bundle that diameter is 5～20 μ m, it is the short fiber bundle of 3～6mm that fiber beam cutting is become average length, be placed on sintering under the vacuum environment of 1000 ℃～1200 ℃ through bulk processing again, obtaining thickness is 0.15～0.25mm, mutually intersects to form the stainless steel short fiber sintering felt in space between the fiber in fiber sintering felt serving;
Described bulk processing refers to: the short fiber bundle is placed in aqueous medium, become the ultimate fibre state to be prepared into uniform aaerosol solution the fibre bundle shredding, and make the short fiber natural subsidence present in a jumble under action of gravitation to arrange, the moisture evaporation is namely obtained fluffy isotropic short fiber layers;
The fiber porosity of described plated film stainless steel short fiber sintering felt integral body is 70%～85%, and the aperture is between 5～50 μ m, and air permeability is 40L/mindm
2Above, thickness direction resistivity is 50～80 μ Ω cm, and face direction thermal conductivity is 15～21W/mK, and yield strength is more than 200MPa, and tensile strength is more than 400MPa.
2. the preparation method of the metal gas diffusion layer for fuel cell according to claim 1, it is characterized in that, described closed field unbalanced magnetron sputtering ion plating technique refers to: the argon gas of employing 99.99% purity and the helium of 99.99% purity are evacuated pressure lower than 3.0 * 10 as sputter gas with furnace chamber
-3Handkerchief, then remove the fiber passivation layer with ar atmo bombardment stainless steel short fiber sintering felt, again take the chromium of 99.99% purity as the plated surface one deck chromium layer of target at stainless steel short fiber sintering felt, then take the graphite of 99.99% purity as target in fibrofelt plated surface one deck graphite linings.
3. the preparation method of the metal gas diffusion layer for fuel cell according to claim 1 and 2, is characterized in that, the thickness of described chromium layer is 0.2 μ m, and the thickness of described graphite linings is 1 μ m.
4. the preparation method of the metal gas diffusion layer for fuel cell according to claim 1, is characterized in that, described hydrophobic is processed and referred to: adopt the polytetrafluoroethylene emulsified material to soak plated film stainless steel short fiber sintering felt integral body by baking.
5. the preparation method of the metal gas diffusion layer for fuel cell according to claim 4, is characterized in that, in described polytetrafluoroethylene emulsified material, the average grain diameter of polytetrafluoroethylene is 0.1～0.3 μ m.
6. the preparation method of the metal gas diffusion layer for fuel cell according to claim 1, it is characterized in that, the ultrasonic concussion method of described employing is carried out surperficial powdered carbon coating and referred to: the mixture of water or water and ethanol is as solvent, and powdered carbon mixes the surface that evenly is coated to afterwards the plated film stainless steel short fiber sintering felt of processing through hydrophobic by ultrasonic dispersion as solute with polytetrafluoroethylene.
7. the preparation method of the metal gas diffusion layer for fuel cell according to claim 1, is characterized in that, described powdered carbon adopts acetylene carbon black.
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| GB201121394D0 (en) * | 2011-12-13 | 2012-01-25 | Netscientific Ltd | Proton exchange membrane fuel cell |
| CN103401003B (en) * | 2013-07-17 | 2016-08-17 | 南京大学昆山创新研究院 | Gas diffusion layers of Proton Exchange Membrane Fuel Cells and preparation method thereof |
| GB201405659D0 (en) | 2014-03-28 | 2014-05-14 | Univ Cape Town | Fuel cell MEA with combined metal gas diffusion layer and microporous layer |
| DE102014109071A1 (en) | 2014-06-27 | 2015-12-31 | Inp Greifswald E.V. | Process for the production of gas diffusion electrodes for fuel cells, as well as gas diffusion electrode and fuel cell |
| RU2577860C1 (en) * | 2015-04-22 | 2016-03-20 | Федеральное государственное бюджетное учреждение "Национальный исследовательский центр "Курчатовский институт" | Method for protection from oxidation of bipolar plates and current collectors of electrolysers and fuel elements with solid polymer electrolyte |
| DE102016013185B4 (en) | 2016-11-04 | 2021-07-15 | Gustav Sievers | Process for the production of catalytic layers for electrochemical systems |
| CN106876743B (en) * | 2017-03-16 | 2019-07-23 | 厦门大学 | A kind of fuel battery gas diffusion layer structure |
| CN108470931A (en) * | 2018-03-15 | 2018-08-31 | 大连交通大学 | A kind of fuel cell metal double polar plates surface corrosion-resistant erosion method of modifying |
| CN110311144B (en) * | 2019-06-26 | 2022-07-15 | 一汽解放汽车有限公司 | Anode gas diffusion layer for prolonging service life of metal bipolar plate and preparation method thereof |
| CN113066995B (en) * | 2021-03-23 | 2022-03-08 | 中国科学院化学研究所 | PEM fuel cell, high-toughness porous carbon paper and preparation method thereof |
| CN113113617B (en) * | 2021-06-11 | 2021-12-14 | 武汉氢能与燃料电池产业技术研究院有限公司 | Membrane electrode, fuel cell gas diffusion layer and preparation method thereof |
| CN114824307B (en) * | 2022-03-15 | 2023-10-10 | 上海碳际实业集团有限公司 | Batch hydrophobic treatment method for gas diffusion layers of fuel cells and production line thereof |
| CN114725420B (en) * | 2022-04-28 | 2023-06-09 | 一汽解放汽车有限公司 | Gas diffusion layer, preparation method thereof, membrane electrode assembly and fuel cell |
| CN114899417B (en) * | 2022-04-28 | 2023-12-29 | 一汽解放汽车有限公司 | Fuel cell gas diffusion layer and preparation method thereof |
| CN115663211B (en) * | 2022-11-11 | 2023-09-29 | 上海氢晨新能源科技有限公司 | Gas diffusion layer and fuel cell |
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