CN103956505A - Gas diffusion layer with water retaining property for fuel cell, preparation method of gas diffusion layer, membrane electrode assembly and application - Google Patents
Gas diffusion layer with water retaining property for fuel cell, preparation method of gas diffusion layer, membrane electrode assembly and application Download PDFInfo
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- CN103956505A CN103956505A CN201410204421.6A CN201410204421A CN103956505A CN 103956505 A CN103956505 A CN 103956505A CN 201410204421 A CN201410204421 A CN 201410204421A CN 103956505 A CN103956505 A CN 103956505A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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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
Abstract
The invention relates to a gas diffusion layer with water retaining property for a fuel cell, a preparation method of the gas diffusion layer, a membrane electrode assembly and application. The gas diffusion layer comprises a carbon paper base and a micro-porous layer, wherein the micro-porous layer is formed by a first hydrophobic layer closely adjacent to the carbon paper base, a hydrophilic layer and a second hydrophobic layer closely adjacent to a catalyst layer by overlaying in sequence, the thickness h2 of the hydrophilic layer is 1.5-2.5 times of the thickness h1 of the first hydrophobic layer, and the thickness h3 of the second hydrophobic layer is 2.5-3.5 times of the thickness h1 of the first hydrophobic layer. The gas diffusion layer can achieve good water retaining property, so as to reduce volatilization amount of liquid water and enable the membrane to be kept in a hydration status under a low-humidity condition; the membrane electrode prepared by the gas diffusion layer can be used for a self-humidifying pile, and is particularly used for the cathode side of an air cooling pile to improve the self-humidifying effect.
Description
Technical field
The present invention relates to fuel cell field, relate in particular to a kind of fuel battery gas diffusion layer with water-retaining property and preparation method thereof and membrane electrode assembly and application, use the MEA of this gas diffusion layers assembling can fine tolerance low humidity operational environment, be applicable to from humidification pile especially air-cooled pile.
Background technology
To the research preparation from humidification membrane electrode can for future air-cooled pile application popularization strong basic guarantee is provided, significant to the development of fuel cell stand-by power supply base station.
Proton Exchange Membrane Fuel Cells (Proton exchange membrane fuel cell, PEMFC) is because energy density is high, it is fast to start, the clean pollution-free concern that is subject to researcher.PEMFC for large power outputs such as Commercial Motor Vehicles, generally adopts external humidification and carries out water-cooled with cooling water, and have the system of external high pressure to operate, and its system is very complicated.Yet the real commercialization that realizes fuel cell just must be simplified complicated operating system, constantly reduces Costco Wholesale, increase the power-mass ratio of PEMFC.
In order to reach above-mentioned these requirements, the fuel cell of ability low humidity becomes present study hotspot, wish especially to use the membrane electrode from humidification by the improvement of some conditions, thereby remove complicated humidification subsystem, become portable mobile power generating device, rather than account for the electricity generation system of bulky.At present, the inside, base station at a lot of stand-by power supplies, needs much for low power PEMFC, to carry out system power supply, has very wide market.The air cooling self-humidifying fuel cell pile of normal pressure work and system are just very applicable like this, and its technology is also very simple, but its unique difficult point is exactly membrane electrode used, must be from humidification.
Air cooling self-humidifying fuel cell is different from general water-cooled humidifying type PEM fuel cell, air-cooling electric pile is used anode dead-end to process, exhaust mode is that step venting (purge) can improve the utilization ratio of anode-side hydrogen like this, also can improve the relative humidity of anode-side; Cathode side adopts open cathode construction, by the fan aspirated negative pressure that causes, the function of reacting gas (air) and maintenance voltaic pile normal work temperature is provided for air-cooled pile simultaneously, and negative electrode excess coefficient than the large 20-40 of traditional water-cooling type Proton Exchange Membrane Fuel Cells doubly.The product water of pile cathode side is the unique water source that remains battery operated, and therefore, in air-cooling electric pile, water management requires stricter than general Proton Exchange Membrane Fuel Cells.The research therefore with the membrane electrode of water retaining function has become the most important thing of today, and the improvement of gas diffusion layers focus especially.
Summary of the invention
The present invention aims to provide a kind of fuel battery gas diffusion layer with water-retaining property and preparation method thereof and membrane electrode assembly and application.Use this gas diffusion layers to can be good at water conservation, reduce the volatilization of aqueous water, make film can under low humidity condition, keep relative hydration status.The membrane electrode that uses this gas diffusion layers to prepare can be used in from humidification pile, and the cathode side that is especially applied to air-cooled pile improves water conservation from humidification effect.
The present invention solves the problems of the technologies described above taked technical scheme to be:
A fuel battery gas diffusion layer with water-retaining property, it comprises carbon paper substrate and microporous layers, it is characterized in that, and described microporous layers is by the first hydrophobic layer that is close to carbon paper substrate, and the second hydrophobic layer of hydrophilic layer and next-door neighbour's Catalytic Layer is stacked to constitute successively; The thickness h of described hydrophilic layer
2it is the first hydrophobic layer thickness h
11.5～2.5 times, the thickness h of the second hydrophobic layer
3it is the first hydrophobic layer thickness h
12.5～3.5 times.
In such scheme, the thickness of described carbon paper substrate is 0.25～0.35mm.
In such scheme, the thickness h of described the first hydrophobic layer
1be 0.05～0.07mm; The thickness h of hydrophilic layer
2be 0.08～0.17mm; The thickness h of the second hydrophobic layer
3be 0.13～0.24mm.
In such scheme, described hydrophilic layer contains hydrophilic high polymers, and described hydrophilic high polymers comprises polyvinyl alcohol, the mixing of one or more in polyaniline or perfluorinated sulfonic resin.
In such scheme, described hydrophilic high polymers is perfluorinated sulfonic resin.
In such scheme, when the humidity of battery operation is 20%～40% time, the quality percentage composition 15～25% of perfluorinated sulfonic resin in hydrophilic layer; When the humidity of battery operation is no more than 20%, in hydrophilic layer, the quality percentage composition of perfluorinated sulfonic resin is 35～45%.
In such scheme, the hydrophobic deg of described carbon paper own is 25%～35%.
In such scheme, all contain hydrophobic high polymer and graphitization carbon dust in described the first hydrophobic layer and the second hydrophobic layer, described hydrophobic high polymer is polytetrafluoroethylene, polymethyl methacrylate or polyethylene; Wherein the hydrophobic deg of the first hydrophobic layer and the second hydrophobic layer is 15%～25%.
In such scheme, the carbon content > 99.5% of described graphitization carbon dust, crystal particle diameter 0.015～0.02mm.
The preparation method of above-mentioned fuel battery gas diffusion layer, it comprises the following steps:
1) carbon paper substrate is carried out to hydrophobic treatment;
2) preparation hydrophilic layer solution, described hydrophilic layer solution makes after being mixed by hydrophilic high polymers, carbon dust and water;
3) prepare the first identical hydrophobic layer and the second hydrophobic layer solution, described the first hydrophobic layer and the second hydrophobic layer solution are obtained by mixing by ptfe emulsion and graphitization carbon dust and water;
4) the first hydrophobic layer is coated in carbon paper substrate in 350～380 ℃ of sintering 20-30min; Again hydrophilic layer solution is coated on the first hydrophobic layer to 80 ℃～140 ℃ sintering 20-30min; Finally the second hydrophobic layer is coated on hydrophilic layer in 350～380 ℃ of sintering 20-30min, described in obtaining, there is the fuel battery gas diffusion layer of water-retaining property.
For a membrane electrode assembly for fuel cell, it comprises gas diffusion layers, and described gas diffusion layers is above-mentioned fuel battery gas diffusion layer.
The application of above-mentioned fuel battery gas diffusion layer in air cooling self-humidifying proton exchange film fuel cell.
For the structure of this gas diffusion layers, do following explanation:
1. for described fuel battery gas diffusion layer, it is characterized in that the close and distant water-bound of " sandwich " type.This patent is selected this structure, is closely-related with the aqueous vapor two-phase transporting mechanism of porous media.As shown in Figure 1, for the transmission characteristic of aqueous water in close and distant water hole, for hydrophilic pores liquid phase, more easily enter aperture, for weep hole liquid phase, more easily enter macropore.(r > 0 is weep hole to be illustrated in figure 2 the relation of aperture and material hydrophilic and hydrophobic and water saturation pressure; R < 0 is hydrophilic pores), can find out, the rate of volatilization of vaporous water has much relations with pore size, with square doubly volatilizing of radius, the water saturation pressure of hydrophilic layer is necessarily lower than hydrophobic layer, and vaporous water easily condenses in hydrophilic pores and water conservation.To sum up analyze, the contiguous Catalytic Layer of the second hydrophobic layer (c), adopts graphitization carbon dust to mix hydrophobic high polymer preparation.Product water in fuel cell Catalytic Layer is vaporous water, adopt after graphited carbon dust the particle diameter of particle less, gas phase is not easy volatilization, so vaporous water more easily liquefies and rests in Catalytic Layer, moistening and the hydrability that keeps film, and with weep hole be allow aqueous water be also not easy through; Hydrophilic layer (b) is at mid portion, and the water that object diffuses out the second hydrophobic layer (c) can be condensate in hole as far as possible, and only has the hydrophilic pores of use can reach such effect; The first hydrophobic layer (a) next-door neighbour carbon paper, adopts graphitization carbon dust to mix hydrophobic layer prepared by hydrophobic high polymer, carries out the further protection of moisture." sandwich " type microporous layers water conservation effect of combination is according to theory analysis and verification experimental verification best results like this.
2. for described fuel battery gas diffusion layer, it forms the thickness h of the hydrophilic layer (b) of microporous layers
2it is the first hydrophobic layer (a) thickness h
11.5～2.5 times, the thickness h of the second hydrophobic layer (c)
3it is the first hydrophobic layer (a) thickness h
12.5～3.5 times; Preferably, coated the first hydrophobic layer (a), hydrophilic layer (b), the thickness proportion of the second hydrophobic layer (c) is 1:2:3.The thickness of every one deck all has corresponding requirement, the thickness h of the first hydrophobic layer (a)
1be 0.05～0.07mm; The thickness h of hydrophilic layer (b)
2be 0.08～0.17mm; The thickness h of the second hydrophobic layer (c)
3be 0.13～0.24mm, this thickness is to need the humidity of work relevant with fuel cell.The maximum that is regulation at the thickness that adds required each close and distant water layer under the condition that humidity is minimum, water retention property is best like this.Thickness is thicker in proportion, and the effect of the resistance to low humidity of its water conservation is better.In the ordinary course of things, the thickness h of the first hydrophobic layer (a)
1for 0.07mm, the thickness h of hydrophilic layer (b)
2for 0.14mm, the thickness h of the second hydrophobic layer (c)
3can resistance to 20% during for 0.21mm and lower low humidity, but gas-premeable is general, but in air-cooled pile, due to the large excess coefficient of negative electrode, so the thickness h of the first hydrophobic layer (a)
1for 0.06mm, the thickness h of hydrophilic layer (b)
2for 0.12mm, the thickness h of the second hydrophobic layer (c)
3low humidity that can substantially resistance to 30% during for 0.18mm, gas permeability still can; The thickness h of the first hydrophobic layer (a)
1for 0.05mm, the thickness h of hydrophilic layer (b)
2for 0.10mm, the thickness h of the second hydrophobic layer (c)
3low humidity that can resistance to 40% during for 0.15mm, good air permeability.The carbon paper of resistance to low humidity is not more thick better, and the thickness of each layer of microporous layers of brushing neither be more thick better, according to the best low humidification water conservation thickness that is stated as above.Cathode side in air-cooled pile, because it is open design, excess coefficient is large, and therefore adopting the carbon paper of large thickness and microporous layers is optimal selection.
3. for carbon paper thickness, our requirement is 0.25mm～0.35mm.The carbon paper thickness generally using for Proton Exchange Membrane Fuel Cells differs larger, has thin carbon paper to be less than 0.2mm, and comprising toray carbon paper and Mitsubishi carbon paper, its thickness is all in 0.2mm left and right; But also have carbon paper that relative thickness is large in 0.3mm left and right, for better water conservation and and the coupling of microporous layers, patent of the present invention is selected the thick carbon paper about 0.3mm.
4. the hydrophilic layer (b) of preparation contains hydrophilic high polymers, and described hydrophilic high polymers comprises polyvinyl alcohol (PVA), the mixing of one or more in polyaniline (PANI) or perfluorinated sulfonic resin; The selection of hydrophilic high polymers is most important, and the different solution containing hydrophilic high polymers have different effects.Conventional hydrophilic high polymers has hydroxyethyl methacrylate (HEMA), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyaniline (PANI), patent of the present invention is preferably used perfluorinated sulfonic resin as the hydrophilic high mol in hydrophilic layer solution.The solution that applies hydrophilic layer comprises hydrophilic perfluor sulfoacid resin solution, commercial carbon dust (also can be described as carbon black) and deionized water.According to battery operated humidity requirement, needing configuration quality mark is 15%～25% and 35%～45% hydrophilic perfluorinated sulfonic resin.Under relative low humidity condition (20%～40%), the perfluorinated sulfonic resin of hydrophilic layer used (solid content 5%) quality percentage composition is 15%～25% just can reach requirement; But under the low humidified condition of extreme (< 20%), the perfluorinated sulfonic resin of hydrophilic layer used (solid content 8%～10%) quality percentage composition will reach 35～45%; The spraying effect of hydrophilic layer solution is good, and the sintering temperature of hydrophilic layer is 80 ℃～140 ℃, and sintering time is 20～30min.At configuration hydrophilic high polymers, be wherein that quality percentage composition is while being 20% hydrophilic layer solution, commercial perfluorinated sulfonic resin can be good at mixing with carbon dust, if ratio is the commercial perfluor sulfoacid resin solution (solid content 5%) of 1g, add 0.2g general commercial carbon dust, 0.5g deionized water; When configuration quality percentage composition is 40% hydrophilic layer solution, commercial perfluorinated sulfonic resin but can not be well and carbon dust mixing, need to concentrate, therefore need to add thermal agitation two hours at 90 ℃, adopt the mode of evaporation and concentration, now add the deionized water of corresponding proportion, ratio is the perfluor sulfoacid resin solution (solid content 10%) after 1g concentrates, add 0.15g general commercial carbon dust and 0.2g deionized water, after stirring, can spray, last sintering.Wherein hydrophilic high polymers is that quality percentage composition is that 20% and 40% hydrophilic layer solution refers to perfluorinated sulfonic resin dry and accounts for 20% and 40% of dry gross mass in hydrophilic layer solution.
5. the hydrophobic deg of carbon paper own is 30%, carbon paper itself is used the large hydrophobic water conservation that is beneficial to gas diffusion layers, ptfe emulsion (mass concentration is 80%) is diluted to 15%, then after thick carbon paper (0.25-0.35mm) being put into configured polytetrafluoroethylene (PTFE) emulsion 8min, take out, in air, hang 10min, then put into the baking oven drying and processing 20min of 100 ℃, obtain pretreated carbon paper.Wherein the account form of carbon paper hydrophobic deg is, the quality of naked carbon paper is m
1, the quality of putting into after PTFE emulsion and drying and processing is m
2, hydrophobic deg is (m
2-m
1)/m
1.
6. the first hydrophobic layer (a) and the second hydrophobic layer (c) contain hydrophobic high polymer, and described hydrophobic high polymer comprises polytetrafluoroethylene (PTFE), polymethyl methacrylate (PMMA) or polyethylene (PE); That the hydrophobic layer of patent of the present invention is used is polytetrafluoroethylene (PTFE), wherein the PTFE hydrophobic deg of two-layer hydrophobic layer is 15%～25%, and 15% or 25% hydrophobic deg refers to dry polytetrafluoroethylene (PTFE) and accounts for 15% or 25% of dry gross mass in hydrophobic layer solution; The sintering temperature of hydrophobic layer is 350 ℃～380 ℃.The common carbon dust of commercialization that the carrier wherein mixing with it typically uses is in the prior art all nutty structures; And this patent is used, be graphitization carbon dust, be common carbon dust through the layer structure of graphitization processing, particle diameter is thinner, particle is less.The requirement that wherein selected graphite powder need to reach is fixed carbon content > 99.5%; Density 0.7g/cm
3; Crystal particle diameter 0.015～0.02mm.
Beneficial effect of the present invention is: use gas diffusion layers of the present invention to can be good at water conservation, reduce the volatilization of aqueous water, make film can under low humidity condition, keep relative hydration status.The membrane electrode that uses this gas diffusion layers to prepare can be used in from humidification pile, and the cathode side that is especially applied to air-cooled pile improves water conservation from humidification effect.
Accompanying drawing explanation
Fig. 1 is the transmission characteristic figure of aqueous water in close and distant water hole.
Fig. 2 is the graph of a relation of aperture and material hydrophilic and hydrophobic and water saturation pressure.
Fig. 3 is the structure chart of gas diffusion layers of the present invention.
Fig. 4 is embodiment 1,2 and 3 and the battery performance comparison diagram of comparative example 1,2 and 3.
Fig. 5 is the battery performance comparison diagram of embodiment 1 and comparative example 4,5.
Embodiment
Below in conjunction with drawings and Examples, illustrate content of the present invention.For a person skilled in the art, be not difficult to find out that the present invention has many improvement and alternative form, as long as they do not deviate from scope of the present invention and principle, should be appreciated that the present invention is not subject to the restriction of following illustrative embodiments.
Embodiment 1
The present embodiment provides a kind of preparation method with the fuel battery gas diffusion layer of water-retaining property, and it comprises the following steps:
1) ptfe emulsion (mass concentration is 80%) is diluted to 15%, then take out after putting into configured polytetrafluoroethylene (PTFE) emulsion 8min carbon paper 0.35mm is thick, in air, hang 10min, then put into the baking oven drying and processing 20min of 100 ℃, obtain pretreated hydrophobic deg and be 30% hydrophobic carbon paper, standby;
2) perfluorinated sulfonic resin that is 10% by solid content (the Nafion PFSA5%Dispersions D520 of Dupond company) solution 18.00g, carbon dust 2.7g, deionized water 3.6g, is made into hydrophilic layer solution, standby; The quality percentage composition of described perfluorinated sulfonic resin is 40%;
3) ptfe emulsion is diluted to mass fraction 20%, gets 6.88g graphitization carbon dust, 870ml deionized water, standing 60min, then adds 8.6gPTFE emulsion and 60ml deionized water to be made into hydrophobic layer solution at normal temperatures, standby; Now the hydrophobic deg of hydrophobic layer is 20%;
4) the first hydrophobic layer is coated in carbon paper substrate in 350 ℃ of sintering 30min; Again hydrophilic layer solution is coated on the first hydrophobic layer to 140 ℃ of sintering 20min; Finally the second hydrophobic layer is coated on hydrophilic layer in 350 ℃ of sintering 30min, described in obtaining, there is the fuel battery gas diffusion layer of water-retaining property.As shown in Figure 1, micro cavity layer structures is " sandwich " type: the first hydrophobic layer (a), hydrophilic layer (b), the second hydrophobic layer (c); Wherein the first hydrophobic layer (a) thickness of brushing is 0.06mm, and hydrophilic layer (b) thickness is 0.12mm, and the thickness of the second hydrophobic layer (c) is 0.18mm, microporous layers gross thickness 0.36mm; (h
1: h
2: h
3=1:2:3).
Prepared gas diffusion layers and CCM (GORE.INC., PRIMEASeries5510) assembled battery are tested, assembling MEA, with fuel battery test system G50 test, battery testing condition is: the Pt carrying capacity of MEA is 0.4mg/cm
2, battery testing temperature is 65 ℃, and the relative humidity of hydrogen and air is 20%, and hydrogen and air pressure are normal pressure, snake shape gas flowfield, active area is 25cm
2, the battery performance that the excess coefficient of test condition is 1.5/30 is shown in Fig. 4.The excess coefficient of test condition is that the battery performance of 1.5/2.5 is shown in Fig. 5.
Embodiment 2
The present embodiment provides a kind of preparation method with the fuel battery gas diffusion layer of water-retaining property, and it comprises the following steps:
1) ptfe emulsion (mass concentration is 80%) is diluted to 15%, then take out after putting into configured polytetrafluoroethylene (PTFE) emulsion 8min carbon paper 0.35mm is thick, in air, hang 10min, then put into the baking oven drying and processing 20min of 100 ℃, obtain pretreated hydrophobic deg and be 30% hydrophobic carbon paper, standby;
2) perfluorinated sulfonic resin that is 10% by solid content (the Nafion PFSA5%Dispersions D520 of Dupond company) solution 18.00g, carbon dust 7.2g, deionized water 3.6g, is made into hydrophilic layer solution, standby; The quality percentage composition of described perfluorinated sulfonic resin is 20%;
3) ptfe emulsion is diluted to mass fraction 20%, gets 6.88g graphitization carbon dust, 870ml deionized water, standing 60min at normal temperatures, then add 8.6gPTFE emulsion and 60ml deionized water 350 degrees Celsius of sintering 30 minutes, be made into hydrophobic layer solution, standby; Now the hydrophobic deg of hydrophobic layer is 20%;
4) the first hydrophobic layer is coated in carbon paper substrate in 380 ℃ of sintering 20min; Again hydrophilic layer solution is coated on the first hydrophobic layer to 80 ℃ of sintering 30min; Finally the second hydrophobic layer is coated on hydrophilic layer in 380 ℃ of sintering 20min, described in obtaining, there is the fuel battery gas diffusion layer of water-retaining property.As shown in Figure 1, micro cavity layer structures is " sandwich " type: the first hydrophobic layer (a), hydrophilic layer (b), the second hydrophobic layer (c); Wherein the first hydrophobic layer (a) thickness of brushing is 0.06mm (please revise), and hydrophilic layer (b) thickness is 0.10mm, and the thickness of the second hydrophobic layer (c) is 0.19mm, microporous layers gross thickness 0.35mm; (h
1: h
2: h
3=1:1.7:3.2).
Prepared gas diffusion layers and CCM (GORE.INC., PRIMEASeries5510) assembled battery are tested, assembling MEA, with fuel battery test system G50 test, battery testing condition is: the Pt carrying capacity of MEA is 0.4mg/cm
2, battery testing temperature is 65 ℃, and the relative humidity of hydrogen and air is 20%, and hydrogen and air pressure are normal pressure, snake shape gas flowfield, active area is 25cm
2, the excess coefficient of test condition is 1.5/30, battery performance is shown in Fig. 4.
Embodiment 3
The present embodiment provides a kind of preparation method with the fuel battery gas diffusion layer of water-retaining property, and it comprises the following steps:
1) ptfe emulsion (mass concentration is 80%) is diluted to 15%, then take out after putting into configured polytetrafluoroethylene (PTFE) emulsion 8min carbon paper 0.35mm is thick, in air, hang 10min, then put into the baking oven drying and processing 20min of 100 ℃, obtain pretreated hydrophobic deg and be 30% hydrophobic carbon paper, standby;
2) perfluorinated sulfonic resin that is 10% by solid content (the Nafion PFSA5%Dispersions D520 of Dupond company) solution 18.00g, carbon dust 2.7g, deionized water 3.6g, is made into hydrophilic layer solution, standby; The quality percentage composition of described perfluorinated sulfonic resin is 40%;
3) ptfe emulsion is diluted to mass fraction 20%, gets 6.88g graphitization carbon dust, 870ml deionized water, standing 60min at normal temperatures, then add 8.6gPTFE emulsion and 60ml deionized water 350 degrees Celsius of sintering 30 minutes, be made into hydrophobic layer solution, standby; Now the hydrophobic deg of hydrophobic layer is 20%;
4) the first hydrophobic layer is coated in carbon paper substrate in 370 ℃ of sintering 30min; Again hydrophilic layer solution is coated on the first hydrophobic layer to 100 ℃ of sintering 30min; Finally the second hydrophobic layer is coated on hydrophilic layer in 370 ℃ of sintering 30min, described in obtaining, there is the fuel battery gas diffusion layer of water-retaining property.As shown in Figure 1, micro cavity layer structures is " sandwich " type: the first hydrophobic layer (a), hydrophilic layer (b), the second hydrophobic layer (c); Wherein the first hydrophobic layer (a) thickness of brushing is 0.06mm, and hydrophilic layer (b) thickness is 0.14mm, and the thickness of the second hydrophobic layer (c) is 0.16mm, microporous layers gross thickness 0.36mm; (h
1: h
2: h
3=1:2.3:2.7).
Prepared gas diffusion layers and CCM (GORE.INC., PRIMEASeries5510) assembled battery are tested, assembling MEA, with fuel battery test system G50 test, battery testing condition is: the Pt carrying capacity of MEA is 0.4mg/cm
2, battery testing temperature is 65 ℃, and the relative humidity of hydrogen and air is 20%, and hydrogen and air pressure are normal pressure, snake shape gas flowfield, active area is 25cm
2, the excess coefficient of test condition is 1.5/30, battery performance is shown in Fig. 4.
Comparative example 1
Comparative example 1 is roughly the same with embodiment 1, difference is that the first hydrophobic layer (a) thickness of brushing is 0.07mm, hydrophilic layer (b) thickness is 0.21mm, the thickness of the second hydrophobic layer (c) is 0.14mm, microporous layers gross thickness 0.42mm, wherein the hydrophilic high polymers quality percentage composition of hydrophilic layer is 40%.(h
1：h
2：h
3＝1：3：2)
By prepared gas diffusion layers and CCM (GORE.INC., PRIMEASeries5510) assembled battery is tested, assembling MEA, with fuel battery test system G50 test, battery testing condition is: the Pt carrying capacity of MEA is 0.4mg/cm2, and battery testing temperature is 65 ℃, the relative humidity of hydrogen and air is 20%, hydrogen and air pressure are normal pressure, snake shape gas flowfield, and active area is 25cm
2, the excess coefficient of test condition is 1.5/30, battery performance is shown in Fig. 4.
Comparative example 2
Comparative example 2 is roughly the same with embodiment 1, difference is that the first hydrophobic layer (a) thickness of brushing is 0.12mm, hydrophilic layer (b) thickness is 0.12mm, the thickness of the second hydrophobic layer (c) is 0.12mm, microporous layers gross thickness 0.36mm, wherein the hydrophilic high polymers quality percentage composition of hydrophilic layer is 40%.(h
1: h
2: h
3=2:2:2), the excess coefficient of test condition is 1.5/30, and battery performance is shown in Fig. 4.
Comparative example 3
Comparative example 3 is roughly the same with embodiment 1, difference is that the first hydrophobic layer (a) thickness of brushing is 0.21mm, hydrophilic layer (b) thickness is 0.14mm, the thickness of the second hydrophobic layer (c) is 0.07mm, microporous layers gross thickness 0.42mm, wherein the hydrophilic high polymers quality percentage composition of hydrophilic layer is 40%.(h
1: h
2: h
3=3:2:1), the excess coefficient of test condition is 1.5/30, and battery performance is shown in Fig. 4.
Comparative example 4
Comparative example 4 is roughly the same with embodiment 1, and what difference was that the hydrophobic layer of micro cavity layer structures uses is common carbon dust, rather than graphited carbon dust.The excess coefficient of test condition is for being 1.5/2.5, and test result is shown in Fig. 5.
Comparative example 5
Comparative example 5 is roughly the same with embodiment 1, and difference is that the hydrophilic high polymers that the hydrophilic layer of micro cavity layer structures is chosen is PVP.The excess coefficient of test condition is for being 1.5/2.5, and test result is shown in Fig. 5.
By the comparison between embodiment and comparative example, can find the gas diffusion layers of the sandwich type structure microporous layers formation of this patent design, wherein thickness has corresponding proportion requirement, hydrophilic high polymers choose and how many proportionings has corresponding requirement, these parameters all can affect the water retention property under low humidification, from battery performance Fig. 4,5, can find out, this design can be good at promoting water retention property, under the large excess coefficient of negative electrode, (air-cooled pile condition of work) internal resistance obviously reduces, excellent performance; Under the little excess coefficient of negative electrode, can there is good practical value at the equal excellent performance of low high electric current, especially can be applied in air-cooled pile and generally need to be in the monocell of humidification.
Claims (12)
1. a fuel battery gas diffusion layer with water-retaining property, it comprises carbon paper substrate and microporous layers, it is characterized in that, and described microporous layers is by the first hydrophobic layer that is close to carbon paper substrate, and the second hydrophobic layer of hydrophilic layer and next-door neighbour's Catalytic Layer is stacked to constitute successively; The thickness h of described hydrophilic layer
2it is the first hydrophobic layer thickness h
11.5～2.5 times, the thickness h of the second hydrophobic layer
3it is the first hydrophobic layer thickness h
12.5～3.5 times.
2. fuel battery gas diffusion layer as claimed in claim 1, is characterized in that, the thickness of described carbon paper substrate is 0.25～0.35mm.
3. fuel battery gas diffusion layer as claimed in claim 1, is characterized in that, the thickness h of described the first hydrophobic layer
1be 0.05～0.07mm; The thickness h of hydrophilic layer
2be 0.08～0.17mm; The thickness h of the second hydrophobic layer
3be 0.13～0.24mm.
4. fuel battery gas diffusion layer as claimed in claim 1, is characterized in that, described hydrophilic layer contains hydrophilic high polymers, and described hydrophilic high polymers comprises polyvinyl alcohol, the mixing of one or more in polyaniline or perfluorinated sulfonic resin.
5. fuel battery gas diffusion layer as claimed in claim 4, is characterized in that, described hydrophilic high polymers is perfluorinated sulfonic resin.
6. fuel battery gas diffusion layer as claimed in claim 5, is characterized in that, when the humidity of battery operation is 20%～40% time, and the quality percentage composition 15～25% of perfluorinated sulfonic resin in hydrophilic layer; When the humidity of battery operation is no more than 20%, in hydrophilic layer, the quality percentage composition of perfluorinated sulfonic resin is 35～45%.
7. fuel battery gas diffusion layer as claimed in claim 1, is characterized in that, the hydrophobic deg of described carbon paper own is 25%～35%.
8. fuel battery gas diffusion layer as claimed in claim 1, it is characterized in that, in described the first hydrophobic layer and the second hydrophobic layer, all contain hydrophobic high polymer and graphitization carbon dust, described hydrophobic high polymer is polytetrafluoroethylene, polymethyl methacrylate or polyethylene; Wherein the hydrophobic deg of the first hydrophobic layer and the second hydrophobic layer is 15%～25%.
9. fuel battery gas diffusion layer as claimed in claim 8, is characterized in that, the carbon content > 99.5% of described graphitization carbon dust, crystal particle diameter 0.015～0.02mm.
10. the preparation method of fuel battery gas diffusion layer as claimed in claim 1, is characterized in that, it comprises the following steps:
1) carbon paper substrate is carried out to hydrophobic treatment;
2) preparation hydrophilic layer solution, described hydrophilic layer solution makes after being mixed by hydrophilic high polymers, carbon dust and water;
3) prepare the first identical hydrophobic layer and the second hydrophobic layer solution, described the first hydrophobic layer and the second hydrophobic layer solution are obtained by mixing by ptfe emulsion and graphitization carbon dust and water;
4) the first hydrophobic layer is coated in carbon paper substrate in 350～380 ℃ of sintering 20-30min; Again hydrophilic layer solution is coated on the first hydrophobic layer to 80 ℃～140 ℃ sintering 20-30min; Finally the second hydrophobic layer is coated on hydrophilic layer in 350～380 ℃ of sintering 20-30min, described in obtaining, there is the fuel battery gas diffusion layer of water-retaining property.
11. 1 kinds of membrane electrode assemblies for fuel cell, it comprises gas diffusion layers, it is characterized in that, described gas diffusion layers is the fuel battery gas diffusion layer described in claim 1-9 any one.
12. the application of the fuel battery gas diffusion layer as described in 1-9 any one in air cooling self-humidifying proton exchange film fuel cell.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107039192A (en) * | 2016-02-02 | 2017-08-11 | 昆明纳太科技有限公司 | The different Buckie paper of two sides hydrophobe, preparation method and applications |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101141002A (en) * | 2006-09-07 | 2008-03-12 | 通用汽车环球科技运作公司 | Fuel cell microporous layer including particles with a controlled pore size distribution |
| CN101252196A (en) * | 2007-02-22 | 2008-08-27 | 通用汽车环球科技运作公司 | Gas diffusion layer with controlled diffusivity over active area |
| US20080299430A1 (en) * | 2004-06-21 | 2008-12-04 | Nissan Motor Co., Ltd. | Gas Diffusion Electrode and Solid Polymer Electrolyte Fuel Cell |
| CN102163723A (en) * | 2010-02-19 | 2011-08-24 | 通用汽车环球科技运作有限责任公司 | High tortuosity diffusion medium |
-
2014
- 2014-05-14 CN CN201410204421.6A patent/CN103956505B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080299430A1 (en) * | 2004-06-21 | 2008-12-04 | Nissan Motor Co., Ltd. | Gas Diffusion Electrode and Solid Polymer Electrolyte Fuel Cell |
| CN101141002A (en) * | 2006-09-07 | 2008-03-12 | 通用汽车环球科技运作公司 | Fuel cell microporous layer including particles with a controlled pore size distribution |
| CN101252196A (en) * | 2007-02-22 | 2008-08-27 | 通用汽车环球科技运作公司 | Gas diffusion layer with controlled diffusivity over active area |
| CN102163723A (en) * | 2010-02-19 | 2011-08-24 | 通用汽车环球科技运作有限责任公司 | High tortuosity diffusion medium |
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