CN111162285B - Conductive gas diffusion layer of fuel cell and preparation method thereof - Google Patents
Conductive gas diffusion layer of fuel cell and preparation method thereof Download PDFInfo
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- CN111162285B CN111162285B CN201811327143.8A CN201811327143A CN111162285B CN 111162285 B CN111162285 B CN 111162285B CN 201811327143 A CN201811327143 A CN 201811327143A CN 111162285 B CN111162285 B CN 111162285B
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Images
Classifications
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a fuel cell conductive gas diffusion layer and a preparation method thereof, wherein the diffusion layer comprises a porous conductive substrate and a conductive porous microporous layer attached to at least one side of the porous conductive substrate, and the porous conductive substrate is a carbon fiber fabric, a carbon paper or a carbon cloth; the carbon fiber fabric is woven or non-woven. The method realizes the uniform distribution of the electronic conductive material and the hydrophobic high molecular binder in the microporous layer on the micro-nano scale, avoids the local agglomeration and phase separation of the two, has accurate and controllable composition and structure on the micro-nano scale of the microporous layer of the prepared gas diffusion layer, can be designed at will to meet the functional requirements of gas-liquid transmission of the gas diffusion layer, and avoids the flooding of the fuel cell in the discharging process.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a gas diffusion layer, a preparation method thereof and a fuel cell.
Background
The fuel cell is an electrochemical reaction device which directly converts chemical energy of fuel molecules into electric energy, and has the advantages of high energy efficiency, small environmental pollution and the like. Compared with other types of fuel cells, the anode reaction of the proton exchange membrane fuel is the oxidation reaction of hydrogen, the cathode reaction of oxygen, and the discharged product is water, so that the proton exchange membrane fuel is a clean energy and is expected to be widely applied to vehicle-mounted power, military equipment, mobile and portable energy equipment.
The membrane electrode is the core component of the proton exchange membrane fuel cell and mainly comprises a solid proton exchange membrane, a catalyst layer and a gas diffusion layer. The porous gas diffusion layer mainly plays a role in supporting a catalyst layer and stabilizing an electrode structure in the membrane electrode, and simultaneously provides a plurality of functions such as reactant introducing and distributing channels, electronic channels and product discharging channels for electrode reaction, and is one of core components of the membrane electrode. The common gas diffusion layer comprises a conductive substrate and a microporous layer, wherein the common substrate materials comprise carbon fiber paper, carbon fiber cloth, carbon fiber felt and the like, and the common substrate materials mainly have the function of supporting, so that the gas diffusion electrode has certain mechanical strength and shape; the microporous layer is typically formed by applying a mixture of a hydrophobic polymeric binder and conductive carbon particles to a conductive substrate by screen printing, spraying or coating processes. In the discharging process of the fuel cell, the gas diffusion layer needs to discharge the generated product water out of the cell in time while introducing and distributing the reaction gas (hydrogen and air) so as to prevent the generated water vapor from condensing into water drops to block the pore channels of the gas diffusion layer, further influence the supply of the reaction gas to the catalyst layer and the catalyst surface, cause flooding of the electrode, and influence the discharging performance and the service life of the cell.
In order to avoid flooding of the electrode, it is necessary to develop a high-performance gas diffusion layer that has good water drainage while maintaining good gas diffusion performance. The current common strategy is to apply PTFE impregnated hydrophobic treatment through the conductive substrate or microporous layer to increase hydrophobicity. Because the diameter of the carbon fiber of the supporting layer is relatively large (8-10um), the pore diameter of the correspondingly formed supporting layer is also large, even if a part of pore structures are blocked by PTFE (polytetrafluoroethylene) lyophobic treatment, the formed pore structures are still too large (>2um), water vapor is easy to condense in the large pores to form large water drops, so that flooding is caused, and the diffusion of reaction gas is influenced. The microporous layer can partially fill and level the macroporous structure of the supporting layer, and the roughness and the porous structure of the supporting layer are reduced. According to the Young-Laplace equation (delta p is gamma/r), the larger the radius of the hydrophobic hole r is, the smaller the surface pressure difference delta p between the inside and the outside of the liquid is, the more easily the hole is soaked by the liquid, and flooding occurs. The filling leveling based on the microporous layer can effectively reduce the size of the pore channel of the gas diffusion layer, improve the pressure difference between the inside and the outside of the liquid and further improve the drainage capacity of the gas diffusion layer. However, in the structure and the process of the existing gas diffusion layer, a mixture slurry prepared by mechanically mixing PTFE resin and conductive carbon powder is mostly adopted and directly coated on the surface of a supporting layer, and because the conductive carbon powder and a high molecular binder such as PTFE have differences in molecular structure, surface physical property, solubility and the like, the conductive carbon powder and the high molecular binder in a microporous layer prepared by the slurry are easy to agglomerate respectively and phase-split, so that a large number of cracks and a large pore structure are caused on the surface of the microporous layer, the surface roughness is large, uneven agglomeration and coalescence of liquid water are caused, and electrode flooding is caused; meanwhile, the catalyst is wasted (the catalyst filled into the cracks of the microporous layer is ineffective), and the roughness of the surface of the catalytic layer is also induced by the larger surface roughness of the microporous layer, so that an electrolyte membrane is damaged when the electrode is hot-pressed, and the leakage of the membrane electrode is caused.
In order to improve the uniformity of the pore structure of the microporous layer and the surface roughness thereof, patent document 1 (jp 2015-79639 a) proposes a preparation technology of a gas diffusion electrode, which comprises forming a microporous layer on the surface of a support layer by a doctor blade coating method, and then reducing the surface roughness by punch forming, but the pore structure of the microporous layer is easily damaged in the punch forming process, so that the diffusion performance of reaction gas is reduced, and the discharge performance of a battery is further influenced; chinese patent No. CN107851805 discloses a method for improving the surface roughness of a gas diffusion layer by constructing a dual microporous layer strategy, wherein the first microporous layer in contact with a conductive substrate layer mainly comprises conductive carbon spheres, and the second microporous layer comprises a conductive material with a linear structure (the aspect ratio of the linear conductive material is 30-5000). According to the scheme, either the forming process of the gas diffusion layer is adopted, or the structure composition of the gas diffusion layer is adjusted, the microporous layer is changed from a single layer to multiple layers, the roughness of the surface of the microporous layer is reduced, the regulation and control of the macroscopic pore structure and the roughness of the microporous layer are strengthened in the aspect of adjusting the micro-area components/structures of the main components of the microporous layer, the designability of the gas diffusion layer is low, and the calculation and the optimization design are difficult to be carried out by combining the theoretical simulation technology of material transfer.
Disclosure of Invention
The invention provides a conductive gas diffusion layer of a fuel cell and a preparation method thereof, which can overcome the problems and defects in the prior art. The gas diffusion layer takes porous carbon paper or carbon cloth as a substrate material, and the uniform distribution of a conductive carbon material and a hydrophobic binder in a microporous layer is improved by regulating and controlling the slurry composition and the preparation method of the microporous layer, so that the uniform distribution of the conductive carbon material and the hydrophobic high molecular binder in the microporous layer on a micro-nano scale is realized, and the local agglomeration and phase separation of the conductive carbon material and the hydrophobic high molecular binder are avoided; the prepared microporous layer of the gas diffusion layer can realize accurate and controllable composition and structure on micro-scale and nano-scale, and can be designed at will to meet the functional requirements of gas-liquid transmission for the gas diffusion layer; the uniform distribution of the high molecular binder in the microporous layer is beneficial to the formation of a gas diffusion layer hydrophobic network, so as to avoid flooding in the discharge process of the fuel cell; in addition, the gas diffusion layer obtained based on the microporous layer slurry and the preparation method has small surface roughness, and the electrolyte membrane damage phenomenon in the hot pressing forming process of the membrane electrode is avoided.
In one aspect, the present invention provides a fuel cell conductive gas diffusion layer comprising a porous conductive substrate, and further comprising an electrically conductive porous microporous layer attached to at least one side of the porous conductive substrate; the porous conductive substrate is a carbon fiber fabric, carbon paper or carbon cloth; the carbon fiber fabric is woven or non-woven.
Based on the technical scheme, preferably, the conductive porous microporous layer consists of a conductive carbon material and a high molecular binder; the mass ratio of the conductive carbon material to the polymer binder is 6:4-9: 1. The conductive carbon powder and the macromolecular binder in the microporous layer of the gas diffusion layer are uniformly distributed on a micro-nano scale, and the components do not have local agglomeration and phase separation behaviors.
Based on the technical scheme, it is further preferable that the conductive carbon material is one or a mixture of more than two of conductive activated carbon, graphite, multi-walled carbon nanotubes, single-walled carbon nanotubes, graphene, reduced graphite oxide and conductive carbon aerosol; the polymer binder is one or a mixture of more than two of polytetrafluoroethylene, polyvinylidene fluoride and derivatives with similar structures.
Based on the technical scheme, it is further preferable that the conductive carbon material and the polymer binder are uniformly distributed on the nano scale of the porous microporous layer, and the particle size of the polymer binder is 50-300 nm.
Based on the technical scheme, it is further preferable that the conductive carbon material and the polymer binder are uniformly distributed on the nano scale of the porous microporous layer, and the particle size of the polymer binder is 50-100 nm.
Based on the technical scheme, the diameter of the carbon fiber fabric is preferably 5-15um, and the length of the carbon fiber fabric is preferably 100-1000 um.
The invention also provides a preparation method of the conductive gas diffusion layer of the fuel cell, which comprises the following steps:
(1) soaking the porous conductive substrate in a macromolecular binder aqueous solution, adsorbing for 5-10min at room temperature, taking out and drying to obtain the porous conductive substrate soaked with the macromolecular binder;
(2) dispersing a conductive carbon material, a high-molecular binder solution and a water-soluble surfactant in an aqueous solution, fully mixing and stirring, heating to 50-90 ℃, continuously mechanically stirring for 1-2 hours, cooling to room temperature, performing solid-liquid separation to obtain a filter cake of microporous layer slurry, dispersing the filter cake in an alcohol-water mixed solution, performing uniform ultrasonic dispersion, and coating the filter cake on the porous conductive substrate impregnated with the high-molecular binder in the step (1) to obtain a gas diffusion layer precursor;
(3) and drying the gas diffusion layer precursor in an oven, then rolling and leveling the gas diffusion layer, and continuing to perform heat treatment to reduce the roughness of the surface of the microporous layer and remove a surfactant, and simultaneously fusing the conductive substrate and the high-molecular binder in the microporous layer into a three-dimensional network to obtain the integrated gas diffusion layer.
Based on the above technical scheme, preferably, the heat treatment temperature in the step (3) is 200-400 ℃, and the treatment time is 10-60 min; the heat treatment is carried out by one or more than two mixed gases of air, oxygen, argon and nitrogen.
Based on the technical scheme, preferably, the concentration of the water-soluble surfactant in the reaction system 1 is 0.01-1000 mmol/L; the reaction concentration of the conductive carbon material in the reaction system 1 is 0.1g/L-2 g/L; the concentration of the macromolecular binder in a reaction system is 0.01g/L-0.2 g/L.
Based on the technical scheme, preferably, the water-soluble surfactant is one or a mixture of more than two of cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, potassium stearate, sodium oleoyl polyamino acid, sodium dodecyl aminopropionate, sodium lauryl sulfate, polyethylene oxide lauroyl ether, sorbitan laurate, diethanolamide oleate, dodecyl dimethyl betaine, tetradecyl dimethyl sulfoethyl betaine, derivatives and analogs thereof. Based on the above technical scheme, it is further preferable that the temperature of the heat treatment is 300-340 ℃; the time of the heat treatment is 20-50 minutes.
Advantageous effects
(1) The method realizes the uniform dispersion and mixing of the conductive carbon material and the hydrophobic high molecular binder by virtue of the action of the water-soluble surfactant in the preparation process of the microporous layer slurry, and the electronic conductive material and the hydrophobic high molecular binder in the conductive porous microporous layer prepared based on the slurry are uniformly distributed on a micro-nano scale, so that the local agglomeration and phase separation of the conductive carbon material and the hydrophobic high molecular binder are effectively avoided; the uniform distribution of the high molecular binder in the microporous layer is beneficial to the formation of a gas diffusion layer hydrophobic network, the composition and the structure of the microporous layer of the gas diffusion layer prepared based on the microporous layer are accurate and controllable in micro-scale and nano-scale, and the microporous layer can be designed at will to meet the functional requirements of gas-liquid transmission of the gas diffusion layer and avoid flooding in the discharging process of the fuel cell.
(2) The gas diffusion layer obtained based on the method has small surface roughness, and can avoid the damage phenomenon of an electrolyte membrane in the membrane electrode forming process.
Drawings
Fig. 1 is a microscopic structure view of a microporous layer of a gas diffusion layer prepared in comparative example 1.
Fig. 2 is a microscopic structure view of the gas diffusion layer prepared in example 1.
Detailed Description
Comparative example 1
Cutting 5cm by 5cm of conductive carbon paper Toray060, then soaking the conductive carbon paper Toray060 in 5 wt% of PTFE aqueous solution (100ml), taking out the conductive carbon paper after 5min, drying the conductive carbon paper for later use by a blower, placing the conductive carbon paper in a high-temperature furnace, and carrying out heat treatment at 340 ℃ in an air atmosphere to ensure that the Toray060 carbon paper has hydrophobicity; 50mg of XC-72R conductive carbon black and 200mg of PTFE aqueous solution (the concentration is 5 wt%) are dispersed in 5ml of ethanol, and after uniform ultrasonic dispersion, the mixture is kept stand for 30min, then the supernatant is removed to obtain microporous layer slurry, the slurry is uniformly coated on one side of hydrophobic Toray060 carbon paper by a blade coating method, and then heat treatment is carried out, wherein the treatment temperature is 350 ℃, the atmosphere is air, and the treatment time is 30 min. By SEM characterization of the gas diffusion layer, the microstructure is shown in FIG. 1, and the microporous layer is found to have uneven surface on the carbon paper support layer and a large amount of microporous structure, with a maximum pore size of about 3-5 μm.
Example 1
Cutting 5cm by 5cm of conductive carbon paper Toray060, then soaking the conductive carbon paper Toray060 in 5 wt% of PTFE aqueous solution (100ml), taking out after 5min, and drying the conductive carbon paper by using a blower for standby; dispersing 50mg of XC-72R conductive carbon black and 200mg of PTFE aqueous solution (the concentration is 5 wt%) in 50ml of aqueous solution, after uniform ultrasonic dispersion, adding 10mg of sodium dodecyl sulfate, continuing to stir for 30min, heating the mixed solution to 80 ℃, continuing to mechanically stir for 2 h, reducing the temperature, filtering the obtained solution to obtain a wet filter cake with the water content of 40%, putting the wet filter cake into 4ml of ethanol-water mixed solution for ultrasonic dispersion to obtain microporous layer slurry, uniformly coating the slurry on one side of hydrophobic Toray060 carbon paper by using a blade coating method, drying the water in an oven, rolling and leveling the slurry, and then putting the Toray060 carbon paper into a certain atmosphere for heat treatment at the treatment temperature of 350 ℃ in the atmosphere of air for 30 min. The gas diffusion layer is characterized by SEM, the microstructure of the gas diffusion layer is shown in figure 2, and the microporous layer can be found to be uniformly distributed on the surface of the carbon paper support layer, the pore structure is relatively uniform and ordered, and the maximum pore diameter is less than 1 micron.
Example 2
Cutting conductive carbon paper SGL 29AA with the thickness of 5cm by 5cm, then soaking the conductive carbon paper SGL 29AA in 5 wt% of PTFE aqueous solution (80ml), taking out after 7min, and drying the conductive carbon paper SGL by using a blower for later use; dispersing 50mg of acetylene black conductive carbon black and 100mg of PTFE aqueous solution (the concentration is 10 wt%) in 50ml of aqueous solution, adding 12mg of polyethylene oxide lauroyl ether after uniform ultrasonic dispersion, continuing to stir for 30min, heating the mixed solution to 60 ℃, continuing to mechanically stir for 1 hour, cooling, filtering the obtained solution to obtain a wet filter cake with the water content of 40%, placing the filter cake in 5ml of ethanol-water mixed solution for ultrasonic dispersion to obtain microporous layer slurry, uniformly coating the slurry on one side of hydrophobic SGL 29AA carbon paper by using a blade coating method, drying the water in an oven, rolling and flattening the water, then placing the mixture in a certain atmosphere for heat treatment, wherein the treatment temperature is 300 ℃, and the atmosphere is the mixture of air and argon (the volume ratio is 1:1) for 30 min. The obtained microporous layer in the gas diffusion layer is uniformly distributed on the surface of the carbon paper support layer, the pore structure is relatively uniform and ordered, and the maximum pore diameter is not more than 1 micron.
Example 3
Cutting out 5 cm-5 cm conductive carbon fiber cloth, then soaking the conductive carbon fiber cloth in 7 wt% PTFE aqueous solution (100ml), taking out after 10min, and drying by using a blower for later use; dispersing 50mg of acetylene black conductive carbon black and 100mg of PTFE aqueous solution (the concentration is 10 wt%) in 50ml of aqueous solution, adding 8mg of polyethylene oxide lauroyl ether after uniform ultrasonic dispersion, continuing to stir for 30min, heating the mixed solution to 60 ℃, continuing to mechanically stir for 1 h, cooling, filtering the obtained solution to obtain a wet filter cake with the water content of 30%, placing the filter cake in 5ml of ethanol-water mixed solution for ultrasonic dispersion to obtain microporous layer slurry, uniformly coating the slurry on one side of hydrophobic conductive carbon fiber cloth by using a blade coating method, drying the water in an oven, rolling and leveling the hydrophobic conductive carbon fiber cloth, and then placing the hydrophobic conductive carbon fiber cloth in a certain atmosphere for heat treatment at the treatment temperature of 300 ℃ in the atmosphere of oxygen for 50 min. The obtained microporous layer in the gas diffusion layer is uniformly distributed on the surface of the carbon paper support layer, the pore structure is relatively uniform and ordered, and the maximum pore diameter is not more than 1 micron. .
Example 4
Cutting conductive carbon paper SGL 29AA with the thickness of 5cm by 5cm, then soaking the conductive carbon paper SGL 29AA in 5 wt% of PTFE aqueous solution (80ml), taking out after 7min, and drying the conductive carbon paper SGL by using a blower for later use; dispersing 50mg of acetylene black conductive carbon black and 100mg of PTFE aqueous solution (the concentration is 10 wt%) in 50ml of aqueous solution, adding 12mg of polyethylene oxide lauroyl ether after uniform ultrasonic dispersion, continuing to stir for 30min, heating the mixed solution to 70 ℃, continuing to mechanically stir for 1 hour, cooling, filtering the obtained solution to obtain a wet filter cake with the water content of 20%, placing the filter cake in 5ml of ethanol-water mixed solution for ultrasonic dispersion to obtain microporous layer slurry, uniformly coating the slurry on one side of hydrophobic SGL 29AA carbon paper by using a blade coating method, drying the water in an oven, rolling and flattening the water, then placing the mixture in a certain atmosphere for heat treatment, wherein the treatment temperature is 270 ℃, and the atmosphere is the mixture of air and argon (the volume ratio is 1:1) for 30 min. The obtained microporous layer in the gas diffusion layer is uniformly distributed on the surface of the carbon paper support layer, the pore structure is relatively uniform and ordered, and the maximum pore diameter is not more than 800 nanometers.
Example 5
Cutting conductive carbon paper SGL 29AA with the thickness of 5cm by 5cm, then soaking the conductive carbon paper SGL 29AA in 5 wt% of PTFE aqueous solution (80ml), taking out after 7min, and drying the conductive carbon paper SGL by using a blower for later use; dispersing 50mg of acetylene black conductive carbon black and 100mg of PTFE aqueous solution (the concentration is 10 wt%) in 50ml of aqueous solution, adding 12mg of polyethylene oxide lauroyl ether after uniform ultrasonic dispersion, continuing to stir for 30min, heating the mixed solution to 60 ℃, continuing to mechanically stir for 1 hour, cooling, filtering the obtained solution to obtain a wet filter cake with the water content of 60%, placing the filter cake in 5ml of ethanol-water mixed solution for ultrasonic dispersion to obtain microporous layer slurry, uniformly coating the slurry on one side of hydrophobic SGL 29AA carbon paper by using a blade coating method, drying the water in an oven, rolling and flattening the water, and then placing the mixture in a certain atmosphere for heat treatment, wherein the treatment temperature is 350 ℃, the atmosphere is argon (the volume ratio is 1:1), and the time is 20 min. The obtained microporous layer in the gas diffusion layer is uniformly distributed on the surface of the carbon paper support layer, the pore structure is relatively uniform and ordered, and the maximum pore diameter is not more than 900 nanometers.
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