CN115084541A - Modified substrate layer, preparation method, gas diffusion layer, membrane electrode and fuel cell - Google Patents
Modified substrate layer, preparation method, gas diffusion layer, membrane electrode and fuel cell Download PDFInfo
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- CN115084541A CN115084541A CN202210701740.2A CN202210701740A CN115084541A CN 115084541 A CN115084541 A CN 115084541A CN 202210701740 A CN202210701740 A CN 202210701740A CN 115084541 A CN115084541 A CN 115084541A
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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
-
- 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
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a modified substrate layer, a preparation method, a gas diffusion layer, a membrane electrode and a fuel cell, and aims to solve the problems that the porosity and the permeability of the gas diffusion layer are low and the overall performance of the fuel cell is reduced. After a cyclic compression experiment, the gas diffusion layer prepared from the modifier bottom layer has the advantages of transverse tensile strength of 13.2-16.1MPa, longitudinal tensile strength of 8.1-9.8MPa, high strength, porosity of 61.25-70.22%, porosity reduction rate of 6.91-10.58%, high retention rate, voltage of 0.386-0.412V, reduction rate of 22.8-25.0%, low reduction range, high power density of a fuel cell and good performance.
Description
Technical Field
The invention belongs to the technical field of preparation of gas diffusion layers, and particularly relates to a modified substrate layer, a preparation method of the modified substrate layer, a gas diffusion layer, a membrane electrode and a fuel cell.
Background
The gas diffusion layer is a major component of the membrane electrode, and is used in a fuel cell together with a catalyst layer, which can directly convert chemical energy possessed by fuel into electrical energy. The gas diffusion layer comprises a substrate layer and a microporous layer, wherein the substrate layer can be directly contacted with the catalytic layer to play a role in supporting the microporous layer and the catalytic layer and also has the functions of collecting current, conducting gas, discharging water and the like.
At present, the porosity and permeability of the gas diffusion layer are low, so that the overall performance of the fuel cell is reduced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified substrate layer, a preparation method, a gas diffusion layer, a membrane electrode and a fuel cell, which have high porosity and good permeability and improve the power density of the fuel cell. The technical scheme of the invention is as follows:
in one aspect, the present invention provides a modified substrate layer comprising a carbon substrate layer and a composite gel layer supported on the carbon substrate layer, wherein the composite gel layer has a mesh skeleton and a polymer filled in the mesh skeleton.
In some embodiments, the composite gel layer loading is 0.01-1 μ g/cm 2 。
In some embodiments, the composite gel layer has a loading of 0.1 to 0.5 μ g/cm 2 。
In some embodiments, the composite gel layer comprises a polyacrylamide-alginate.
In some embodiments, the polyacrylamide-alginate comprises at least one of polyacrylamide-sodium alginate, polyacrylamide-potassium alginate, and polyacrylamide-calcium alginate.
In some embodiments, the carbon substrate layer has a hydrophobic coating.
In a second aspect, the present invention also provides a method for preparing a modified substrate layer as described above, the method comprising the steps of:
dipping the carbon substrate layer in the composite hydrogel for 20-40min at 20-60 ℃, and then curing to obtain a modified substrate layer; the composite hydrogel is provided with a reticular framework and a polymer filled in the reticular framework.
In some embodiments, the temperature of the dipping treatment is 35-60 ℃ and the time of the dipping treatment is 25-35 min.
In some embodiments, the composite hydrogel comprises a polyacrylamide-alginate hydrogel.
In some embodiments, the polyacrylamide-alginate hydrogel is prepared by a method comprising:
mixing alginate, acrylamide, a first cross-linking agent and an initiator, then dripping an accelerator, stirring and curing for 2.5-3.5h to prepare cross-linked gel;
and (3) placing the crosslinked gel in a second crosslinking agent to be soaked for 18-22min for hybridization to obtain the polyacrylamide-alginate hydrogel.
In some embodiments, the alginate comprises at least one of sodium alginate, potassium alginate, and calcium alginate.
In some embodiments, before the carbon substrate is treated by the composite hydrogel impregnation treatment, the method further comprises the following steps:
and (3) soaking the carbon substrate layer in a hydrophobic agent for 25-35min, and drying at 50-70 ℃ for 50-70 min.
In a third aspect, the present invention also provides a gas diffusion layer comprising:
the modified substrate layer or the modified substrate layer prepared by the preparation method;
a microporous layer overlying the modified base layer.
In a fourth aspect, the present invention further provides a membrane electrode, where the membrane electrode includes the modified substrate layer, or the modified substrate layer prepared by the preparation method, or the gas diffusion layer.
In a fifth aspect, the present invention also provides a fuel cell, which includes the modified substrate layer, or the modified substrate layer prepared by the preparation method, or the gas diffusion layer, or the membrane electrode.
The beneficial effects of the invention at least comprise:
the modified substrate layer provided by the invention comprises a carbon substrate layer and a composite gel layer loaded on the carbon substrate layer, wherein the composite gel layer is provided with a net-shaped framework and a polymer filled in the net-shaped framework. The carbon substrate layer can be carbon paper or carbon fiber and is used as a substrate layer for supporting the microporous layer; the reticular skeleton of the composite gel layer has high hardness and brittleness, the polymer filled in the reticular skeleton has good toughness, the composite gel layer is attached to the carbon substrate, and in the stacking process, if the loading pressure is lower, the hardness of the reticular skeleton is higher than the loading pressure, so that the structure of the substrate layer can be ensured not to be damaged, the microporous layer attached to the modified substrate layer is ensured not to be damaged, namely the structures of the air holes and the liquid through holes of the microporous layer are protected, and the porosity of the gas diffusion layer is ensured; if the loading pressure is larger, because the inside of the reticular skeleton is provided with the tough polymer, the gas diffusion layer prepared by the modified carbon substrate shows good elasticity, under the larger loading pressure, the gas diffusion layer generates micro deformation, only a few reticular skeletons are crushed and attached to the tough polymer inside, the high-strength reticular skeleton continuously provides support, the microstructure of the air holes and the liquid through holes of the microporous layer is prevented from being damaged, the porosity of the gas diffusion layer is ensured, meanwhile, the few damaged reticular skeletons also enable the internal network structure to gradually become compact, the strength is further increased, and further support is provided for the microporous layer. Macroscopically, the gas diffusion layer prepared by the modified substrate layer shows good strength and toughness under the action of repeatedly loaded loading pressure, the porosity of the gas diffusion layer is ensured, the gas diffusion layer has good ventilation and drainage capabilities, the chemical reaction of the fuel cell is ensured to be carried out smoothly, and higher voltage is shown under the same current density, so that the power density of the pile is improved, and the fuel cell has good performance. After a cyclic compression experiment, the gas diffusion layer prepared from the modifier bottom layer has the advantages of transverse tensile strength of 13.2-16.1MPa, longitudinal tensile strength of 8.1-9.8MPa, high strength, porosity of 61.25-70.22%, porosity reduction rate of 6.91-10.58%, high retention rate, voltage of 0.386-0.412V, reduction rate of 22.8-25.0%, low reduction range, high power density of a fuel cell and good performance.
Drawings
FIG. 1 is a diagram showing the steps of a preparation process of polyacrylamide-alginate hydrogel.
Fig. 2 shows polarization curves of the gas diffusion layers of example 1, comparative example 1 and comparative example 2 of the present application before the cyclic compression experiment.
Fig. 3 shows polarization curves of the gas diffusion layers of example 1, comparative example 1 and comparative example 2 of the present application after a cyclic compression experiment.
Detailed Description
In order to make the present application more clearly understood by those skilled in the art to which the present application pertains, the following detailed description of the present application is made with reference to the accompanying drawings by way of specific embodiments.
In the process of stacking the fuel cell, in order to ensure the sealing performance of the fuel cell, fastening and assembling must be performed under a large mounting pressure, and the mechanical strength of the gas diffusion layer is low, the gas diffusion layer is compressed due to the mounting pressure, the structure of the compressed gas diffusion layer is damaged, the porosity of the gas diffusion layer is reduced, the permeability is reduced, and the overall performance of the fuel cell is reduced.
Based on the shortcomings in the prior art, the present application provides a modified substrate layer, a method of preparing the same, a gas diffusion layer, a membrane electrode, and a fuel cell.
In a first aspect, an embodiment of the present application provides a modified substrate layer, which may be used to fabricate a gas diffusion layer, a membrane electrode or a fuel cell, where a composite gel layer having a mesh skeleton and a polymer structure filled in the mesh skeleton is loaded on a carbon substrate, and the composite gel layer has the mesh skeleton to make the carbon substrate layer have good strength, and the polymer filled in the mesh skeleton has elasticity, so that the carbon substrate layer has good toughness, and thus has good mechanical strength and compressive property under repeated press-fitting force in a stack, and the porosity of the gas diffusion layer can be ensured after the stack is stacked, so that the gas diffusion layer has good permeability, and can ventilate and drain smoothly, and the performance of the fuel cell is improved.
The modified substrate layer provided by the embodiment of the application comprises a carbon substrate layer and a composite gel layer loaded on the carbon substrate layer, wherein the composite gel layer is provided with a net-shaped framework and a polymer filled in the net-shaped framework. The carbon substrate layer can be carbon paper or carbon fiber and is used as a substrate layer for supporting the microporous layer; the reticular skeleton of the composite gel layer has high hardness and brittleness, the polymer filled in the reticular skeleton has good toughness, the composite gel layer is attached to the carbon substrate, and in the stacking process, if the loading pressure is lower, the hardness of the reticular skeleton is higher than the loading pressure, so that the structure of the substrate layer can be ensured not to be damaged, the microporous layer attached to the modified substrate layer is ensured not to be damaged, namely the structures of the air holes and the liquid through holes of the microporous layer are protected, and the porosity of the gas diffusion layer is ensured; if the loading pressure is larger, because the inside of the reticular skeleton is provided with the tough polymer, the gas diffusion layer prepared by the modified carbon substrate shows good elasticity, under the larger loading pressure, the gas diffusion layer generates micro deformation, only a few reticular skeletons are crushed and attached to the tough polymer inside, the high-strength reticular skeleton continuously provides support, the microstructure of the air holes and the liquid through holes of the microporous layer is prevented from being damaged, the porosity of the gas diffusion layer is ensured, meanwhile, the few damaged reticular skeletons also enable the internal network structure to gradually become compact, the strength is further increased, and further support is provided for the microporous layer. Macroscopically, the gas diffusion layer prepared by the modified substrate layer shows good strength and toughness under the action of repeatedly loaded loading pressure, the porosity of the gas diffusion layer is ensured, the gas diffusion layer has good ventilation and drainage capabilities, the chemical reaction of the fuel cell is ensured to be carried out smoothly, and higher voltage is shown under the same current density, so that the power density of the pile is improved, and the fuel cell has good performance.
In some embodiments, the composite gel layerThe loading amount of (A) is 0.01-1 mu g/cm 2 . Too high loading of the composite gel layer can cause the base layer, namely the pores of the carbon paper, to be blocked, thereby reducing the number of air holes and liquid through holes in the microporous layer; too low loading of the composite gel layer reduces the porosity improvement effect. Preferably, the loading of the composite gel layer may be 0.1-0.5 μ g/cm 2 More preferably, the loading of the composite gel layer is 0.3 μ g/cm 2 。
Specifically, the composite gel layer comprises polyacrylamide-alginate. The polyacrylamide-alginate has a net-shaped framework and a tough polymer structure filled in the net-shaped framework, and the modified substrate layer has good strength and toughness, so that the good porosity of gas diffusion is ensured in repeated loading and pressing of the fuel cell stack, and the performance of the fuel cell is improved.
In some embodiments, the polyacrylamide-alginate includes at least one of polyacrylamide-sodium alginate, polyacrylamide-potassium alginate, and polyacrylamide-calcium alginate, that is, the polyacrylamide-alginate can be polyacrylamide-sodium alginate, can be polyacrylamide-potassium alginate, and can also be polyacrylamide-calcium alginate, and can of course be any two of the three, and in other embodiments, the polyacrylamide-alginate can also be a mixture of the three.
In some embodiments, the carbon substrate layer has a hydrophobic coating, so that the modified substrate layer has hydrophobicity, and the formed through hole has good drainage capacity, and the service performance of the fuel cell is improved.
In a second aspect, based on the same inventive concept as that of the first aspect, embodiments of the present application further provide a method for preparing the modified substrate layer, so as to prepare the modified substrate layer with good strength and toughness, where a gas diffusion layer prepared by using the modified substrate layer can ensure that a fuel cell has good porosity under repeated loading pressure of a stack, has good ventilation and liquid passing effects, and ensures the use performance of the fuel cell.
The preparation method of the modified substrate layer provided by the embodiment of the application comprises the following steps:
dipping the carbon substrate layer in the composite hydrogel for 20-40min at 20-60 ℃, and then curing to obtain a modified substrate layer; the composite hydrogel is provided with a reticular framework and a polymer filled in the reticular framework.
The carbon substrate may be soaked in the composite hydrogel, or the composite hydrogel may be coated on a hydrophobic carbon substrate, such as by screen printing. The time of the dipping treatment and the temperature of the dipping treatment are controlled, so that the composite hydrogel can be firmly combined on the carbon substrate layer, the pores of the carbon substrate are not blocked, and the effects of improving the strength and the toughness are achieved. The contact time between the hydrophobic carbon substrate and the composite hydrogel is too long, and the pores on the carbon substrate can be blocked due to too much composite hydrogel combined on the hydrophobic carbon substrate; the contact time of the carbon substrate layer and the composite hydrogel is too short, the composite hydrogel combined on the carbon substrate layer is too little, the modification effect cannot be achieved, and the porosity of the gas diffusion layer cannot be ensured. The impregnation treatment temperature of the carbon substrate layer and the composite hydrogel is too high, the combination rate of the water-carbon substrate layer and the composite hydrogel is too high, the uniformity of attachments on the carbon substrate layer is poor, the pore blocking phenomenon of the carbon paper can occur in some positions, and the modification effect is poor in some positions; the dipping treatment temperature of the carbon substrate layer and the composite hydrogel is too low, and the molecular movement rate is slow, so that the time of the composite hydrogel modified carbon substrate layer is prolonged, and the production efficiency is reduced. The curing method may be ultraviolet curing (UV curing) or hot air circulation curing, and is not limited herein.
Preferably, the temperature of the dipping treatment is 35-60 ℃, and the time of the dipping treatment is 25-35 min.
In some embodiments, the composite hydrogel may include a polyacrylamide-alginate hydrogel, which has a mesh-like skeleton at a microscopic level and a flexible polymer structure filled in the mesh-like skeleton, such that the modified substrate layer has good strength and flexibility, and good porosity for gas diffusion is ensured during repeated stacking and loading of the fuel cell, thereby improving the performance of the fuel cell.
In some embodiments, with reference to fig. 1, the steps of preparing the polyacrylamide-alginate hydrogel comprise:
s1, mixing alginate, acrylamide, a first cross-linking agent and an initiator, then dripping an accelerator, stirring and curing for 2.5-3.5h to obtain the cross-linked gel.
The first crosslinking agent may be methylene bis acrylamide (MBAA), the initiator may be Ammonium Persulfate (APS), the accelerator may be Tetramethylethylenediamine (TEMED), and the accelerator may have the same mass as acrylamide. The curing treatment may be a light irradiation treatment.
And S2, soaking the crosslinked gel in a second crosslinking agent for 18-22min, and hybridizing to obtain the polyacrylamide-alginate hydrogel.
The second cross-linking agent can be a calcium chloride solution, and calcium ions in the calcium chloride solution can promote the polymerization of the alginate monomer. Specifically, the concentration of the calcium chloride solution may be 0.03M.
Specifically, the preparation of polyacrylamide-alginate can be obtained by the following method: mixing alginate, acrylamide, Methylene Bisacrylamide (MBAA) and Ammonium Persulfate (APS) solutions, then dropwise adding Tetramethylethylenediamine (TEMED) in the weight of the methylene bisacrylamide, fully stirring, carrying out ultraviolet irradiation treatment on the solution for 3 hours, taking out the gel from a calcium chloride solution, and soaking for 20min to obtain the polyacrylamide-alginate hydrogel.
In some embodiments, the alginate comprises at least one of sodium alginate, potassium alginate, and calcium alginate.
In some embodiments, before the carbon substrate is treated by the composite hydrogel impregnation treatment, the method further comprises the following steps:
and (3) soaking the carbon substrate layer in a hydrophobic agent for 25-35min, and drying at 50-70 ℃ for 50-70 min.
The carbon substrate layer can form a hydrophobic coating on the surface of the carbon substrate after being soaked in the hydrophobic agent, the polyacrylamide-alginate is attached to the carbon substrate layer with the hydrophobic coating, so that the hydrophobic performance can be prevented from being damaged in the press fitting process, if the hydrophobic agent is attached to the polyacrylamide-alginate, the structure of the hydrophobic coating can be damaged in the press fitting process, the hydrophobic effect of air holes and liquid through holes in the microporous layer is reduced, the normal reaction of the fuel cell is influenced, and the power density of the fuel cell is reduced. The water repellent agent is Polytetrafluoroethylene (PTFE), and after hydrophobic treatment, the hydrophobic property of the liquid through hole can be improved, so that the water repellent agent has good drainage capability, and the normal operation of the fuel cell is ensured.
In a third aspect, embodiments of the present application further provide a gas diffusion layer having good strength and toughness, so that good porosity is maintained under repeated press-fitting force during stacking, and power density of a fuel cell is improved.
The gas diffusion layer provided by the embodiment of the application comprises a microporous layer and the modified substrate layer, or the gas diffusion layer comprises the microporous layer and the modified substrate layer prepared by the preparation method, and the microporous layer covers the modified substrate layer.
The preparation method of the gas diffusion layer provided by the embodiment of the application comprises the following steps:
1. preparing microporous layer slurry: mixing a pore-forming agent, a conductive agent, a water repellent and a dispersing agent to prepare microporous layer slurry;
2. preparing a gas diffusion layer: coating the microporous layer slurry on the modified substrate layer, and performing first roasting; and coating the microporous layer slurry on the modified substrate layer after the first roasting, and carrying out second roasting to obtain the gas diffusion layer.
In some embodiments, the conductive agent may include at least one of acetylene black, Vulcan XC-72, carbon nanotubes. The acetylene black is carbon black obtained by continuously pyrolyzing acetylene with purity of more than 99% which is obtained by decomposing and refining by-product gas generated during pyrolysis of calcium carbide method or naphtha (crude gasoline); vulcan XC-72 is a carbon black type produced by Kabot, USA; carbon nanotubes, also known as buckytubes, are one-dimensional quantum materials with a particular structure (radial dimensions are of the order of nanometers, axial dimensions are of the order of micrometers, and both ends of the tube are substantially sealed).
The roasting can be carried out in a drying box or a resistance type heating box; the first roasting time can be 1-3h, and the first roasting temperature can be 250-350 ℃. The first roasting process is controlled, so that a plurality of vent holes and liquid through holes are formed in the holes formed after the pore-forming agent is coated with the polyacrylamide-alginate, and the binding force between the microporous layer and the modified substrate layer is improved. The production efficiency is influenced by too long first roasting time; the first roasting time is too short, and the structures of the air holes and the liquid through holes of the microporous layer are not firm enough and are easy to collapse; the first roasting temperature is too high, so that energy waste is caused; the first roasting temperature is too low, so that the roasting time is prolonged, and the production efficiency is influenced. After the first roasting is finished, coating the microporous layer slurry again and carrying out secondary roasting, namely second roasting, the number of air holes and liquid through holes in the microporous layer can be increased, and the power density of the fuel cell can be improved. In some embodiments, the second calcination time is 2-5h, and the second calcination temperature is 250-350 ℃. Controlling the time for the second firing to be longer than the time for the first firing makes it possible to make all the vent holes and the liquid passing holes structurally strong.
In some embodiments, the mass ratio of the pore-forming agent to the conductive agent to the water repellent to the dispersing agent is (12-200): (3-10): (0.8-1.2): (10-30).
In a fourth aspect, embodiments of the present disclosure also provide a membrane electrode having good strength and compression resistance, and good porosity after stacking, such that the fuel cell has a higher power density.
The membrane electrode provided by the embodiment of the application comprises the modified substrate layer provided by the first aspect, or the modified substrate layer prepared by the preparation method provided by the second aspect, or the gas diffusion layer provided by the third aspect.
In a fifth aspect, embodiments of the present application further provide a fuel cell having good porosity, such that the fuel cell has a higher power density.
The fuel cell provided by the embodiment of the application comprises the modified substrate layer provided by the first aspect, or the modified substrate layer prepared by the preparation method provided by the second aspect, or the gas diffusion layer provided by the third aspect, or the membrane electrode provided by the fourth aspect.
The modified substrate layer and gas diffusion layer of the examples of the present application will be further described with reference to specific examples.
Example 1
Example 1 provides a modified substrate layer and a method for preparing the same, in which carbon paper is placed in a hydrophobic agent PTFE for hydrophobic treatment for 10min, then placed in polyacrylamide-sodium alginate hydrogel at 60 ℃ for 30min, and finally subjected to ultraviolet curing to obtain the modified substrate layer.
Mixing a pore-forming agent ethylene glycol, acetylene black, a water repellent PTFE and a dispersant isopropanol according to a ratio of 12:5:1:12 to prepare microporous layer slurry, coating the microporous layer slurry on a modified substrate layer, roasting for 3 hours, then coating the microporous layer slurry once again, and roasting for 3 hours twice to obtain the gas diffusion layer.
Example 2
Example 2 referring to example 1, example 2 differs from example 1 in that: the contact temperature of the carbon paper and the polyacrylamide-sodium alginate is 35 ℃, and the contact time is 35 min; the other steps in example 2 are the same as in example 1.
Example 3
Example 3 referring to example 1, example 3 differs from example 1 in that: the contact temperature of the carbon paper and the polyacrylamide-sodium alginate is 40 ℃, and the contact time is 20 min; the other steps in example 3 are the same as in example 1.
Example 4
Example 4 provides a modified substrate layer and a method for preparing the same, in which a carbon cloth is placed in a hydrophobic agent PTFE for hydrophobic treatment for 5min, then placed in a polyacrylamide-potassium alginate hydrogel at 60 ℃ for 30min, and finally subjected to ultraviolet curing to obtain the modified substrate layer.
And mixing a pore-forming agent ammonium bicarbonate, a carbon nano tube, a water repellent PTFE and a dispersant oxidized polyethylene wax according to a ratio of 50:8:1:18 to prepare microporous layer slurry, coating the microporous layer slurry on the modified substrate layer, roasting for 2.5 hours, then coating the microporous layer slurry once again, and roasting for 3.5 hours twice to obtain the gas diffusion layer.
Example 5
Example 5 provides a modified substrate layer and a method for preparing the same, in which a carbon cloth is placed in a hydrophobic agent for hydrophobic treatment for 5min, then placed in a polyacrylamide-calcium alginate hydrogel at a temperature of 40 ℃ for 25min, and finally subjected to ultraviolet curing to obtain the modified substrate layer.
Mixing a pore-forming agent lithium carbonate, a carbon nano tube CS1001, a water repellent PTFE and a dispersant polyethylene glycol according to a ratio of 80:5:1:25 to prepare microporous layer slurry, coating the microporous layer slurry on a modified substrate layer, roasting for 2 hours, then coating the microporous layer slurry once again, and roasting for 4 hours twice to obtain the gas diffusion layer.
Comparative example 1
Comparative example 1 provides a method for preparing a gas diffusion layer, comprising the steps of:
1. placing the carbon paper into a hydrophobic agent for hydrophobic treatment;
2. preparing microporous layer slurry: mixing a pore-forming agent isopropanol and Vulcan XC-72 carbon powder in a mass ratio of 3:1, then carrying out magnetic stirring to obtain slurry A, adding a pore-forming agent glycol and PTFE emulsion with solid content of 60% into the slurry A dispersed to a certain degree, continuing carrying out magnetic stirring, and carrying out ball milling to obtain uniformly dispersed microporous layer slurry;
3. preparation of a gas diffusion layer: and (3) performing screen printing on the microporous layer slurry obtained in the step (2) twice, firstly fixing the substrate layer in a magnetic attraction manner, taking out the substrate layer after the first printing is finished, drying the substrate layer in an oven at 60 ℃ for 1h, then putting the substrate layer in a box type resistance furnace, heating the substrate layer to 300 ℃ for roasting the substrate layer for 3h, performing second screen printing, drying the substrate layer in the oven at 60 ℃ for 1h, then putting the substrate layer in the box type resistance furnace, heating the substrate layer to 300 ℃ for roasting the substrate layer for 3h, performing second screen printing, and finally putting the substrate layer in the oven at 60 ℃ for drying for 1h, and then putting the substrate layer in the box type resistance furnace, heating the substrate layer to 300 ℃ for roasting the 3h to obtain the final gas diffusion layer.
Comparative example 2
Comparative example 2 provides a method for preparing a gas diffusion layer, comprising the steps of:
1. preparation of polyacrylamide-ammonium alginate: first, 5g of nano aluminum hydroxide was added to 100mL of deionized water at room temperature, and stirred for 15 min. Subsequently, 5g of ammonium alginate was slowly added and the mixture was continuously stirred to obtain a uniform sol. Pouring the sol into a mould, quickly freezing by using liquid nitrogen, freeze-drying the frozen sample in a freeze dryer at-85 to-95 ℃ for about 72 hours. And finally, transferring the gel into a vacuum oven to be dried for 3h to obtain aerogel, soaking the aerogel in a calcium chloride/ethanol solution for 3h at room temperature to ensure complete crosslinking, and drying the crosslinked sample in the vacuum oven for 24h to remove ethanol to obtain the crosslinked ammonium alginate hydrogel.
2. Pretreatment of the substrate layer: firstly, carbon paper is put into PTFE (polytetrafluoroethylene) solution with the mass fraction of 15% to be soaked, the carbon paper is put into an oven after being soaked for 30 minutes, the carbon paper is dried for 1 hour at the temperature of 60 ℃, the step is repeated, the content of PETF in the pretreated carbon paper is 5.5%, a substrate layer is soaked in alginate-based nano composite aerogel for 30 minutes, the alginate-based nano composite aerogel and the substrate layer are combined in a UV curing mode, and finally the modified substrate layer is obtained, wherein the loading capacity of the alginate-based nano composite aerogel on the substrate layer is 0.1 microgrammes per square centimeter.
3. Preparing microporous layer slurry: mixing a pore-forming agent isopropanol and Vulcan XC-72 carbon powder in a mass ratio of 3:1, then carrying out magnetic stirring to obtain slurry A, adding a pore-forming agent glycol and PTFE emulsion with solid content of 60% into the slurry A dispersed to a certain degree, continuing carrying out magnetic stirring, and carrying out ball milling to obtain uniformly dispersed microporous layer slurry;
4. preparation of a gas diffusion layer: and (3) screen printing the microporous layer slurry obtained in the step (3) twice, firstly fixing the pretreated substrate layer obtained in the step (2) in a magnetic attraction manner, taking out the pretreated substrate layer after the first printing is finished, drying the pretreated substrate layer in an oven at 60 ℃ for 1h, then putting the dried substrate layer in a box type resistance furnace, heating the substrate layer to 300 ℃ for roasting for 3h, carrying out second screen printing, drying the substrate layer in the oven at 60 ℃ for 1h, then putting the dried substrate layer in the box type resistance furnace, heating the substrate layer to 300 ℃ for roasting for 3h, and obtaining the final gas diffusion layer.
Comparative example 3
Comparative example 3 provides a method for preparing a gas diffusion layer, comparative example 3 is referred to example 1, and comparative example 3 is different from example 3 in that: the contact temperature of the carbon paper and the polyacrylamide-sodium alginate is 10 ℃, and the contact time is 10 min; the other steps in comparative example 3 were the same as in example 1.
Comparative example 4
Comparative example 4 provides a method for preparing a gas diffusion layer, comparative example 4 is referred to example 1, and comparative example 4 is different from example 3 in that: the contact temperature of the carbon paper and the polyacrylamide-sodium alginate is 80 ℃, and the contact time is 50 min; the other steps in comparative example 4 were the same as in example 1.
The gas diffusion layers of examples 1 to 5 and comparative examples 1 to 4 were subjected to 10 cycles of a cyclic compression test at a pressure of 1MPa and a holding pressure of 30 s; simultaneously, the gas diffusion layers before and after the cyclic compression experiment are respectively subjected to polarization curve test, and the current of the polarization curve is 2000mA/cm 2 (ii) a The gas diffusion layers before and after the cyclic compression test were subjected to transverse direction (MD), longitudinal direction (TD) tensile strength tests, and tested for porosity, as shown in tables 1 and 2.
TABLE 1
TABLE 2
| Numbering | Rate of voltage decrease/%) | Reduction of porosity/%) |
| Example 1 | 25.0 | 6.91 |
| Example 2 | 22.8 | 6.96 |
| Example 3 | 23.4 | 9.88 |
| Example 4 | 23.3 | 10.58 |
| Example 5 | 24.5 | 8.05 |
| Comparative example 1 | 30.2 | 10.7 |
| Comparative example 2 | 30.1 | 15.61 |
| Comparative example 3 | 28.7 | 13.58 |
| Comparative example 4 | 30.8 | 13.03 |
As can be seen from the data in table 1, the loading amount of the polyacrylamide-alginate in the modified substrate layer provided by the present application is 0.06-0.15 μ g/cm2, the transverse tensile strength of the gas diffusion layer prepared by using the modified substrate layer before the cyclic compression test is 17.1-19.2MPa, the longitudinal tensile strength is 11.9-13.7MPa, the porosity is 67.18-75.43%, and the voltage is 0.511-0.549V; after cyclic compression experiments, the transverse tensile strength is 13.2-16.1MPa, the longitudinal tensile strength is 8.1-9.8MPa, the porosity is 61.25-70.22%, the porosity reduction rate is 6.91-10.58%, the retention rate is high, the voltage is 0.386-0.412V, the reduction rate is 22.8-25.0%, and the reduction amplitude is low.
The gas diffusion layer prepared by the modified substrate layers provided in comparative examples 1 to 4 has a transverse tensile strength of 15.2 to 16.9MPa, a longitudinal tensile strength of 8.5 to 10.3MPa, a porosity of 56.08 to 63.24% and a voltage of 0.467 to 0.509V before a cyclic compression test, which are lower than those of examples 1 to 5 of the present application; after cyclic compression test, transverse tensile strength is 9.2-11.6MPa, longitudinal tensile strength is 3.3-5.7MPa, and porosity is 48.77-53.37%, which is lower than that of the examples 1-5 in the application; the porosity rate is 13.03-15.61%, the retention rate is lower than that of the embodiment 1-5, the voltage is 0.326-0.356V, the voltage rate is lower than that of the embodiment 1-5, the voltage rate is 28.0-30.8%, the reduction range is higher than that of the embodiment 1-5, and the power density is lower than that of the embodiment.
As can be seen from fig. 2 and 3, the voltage before and after the cyclic compression test of example 1 of the present application was higher than that of comparative examples 1 and 2, which are consistent with the data in table 1.
The modified substrate layer provided by the invention comprises a carbon substrate layer and a composite hydrogel layer loaded on the carbon substrate layer, wherein the composite gel layer is provided with a net-shaped framework and a polymer filled in the net-shaped framework. The carbon substrate layer can be carbon paper or carbon fiber and is used as a substrate layer for supporting the microporous layer; the reticular skeleton of the composite gel layer has high hardness and brittleness, the polymer filled in the reticular skeleton has good toughness, the composite gel layer is attached to the carbon substrate, and in the stacking process, if the loading pressure is lower, the hardness of the reticular skeleton is higher than the loading pressure, so that the structure of the substrate layer can be ensured not to be damaged, the microporous layer attached to the modified substrate layer is ensured not to be damaged, namely the structures of the air holes and the liquid through holes of the microporous layer are protected, and the porosity of the gas diffusion layer is ensured; if the loading pressure is larger, because the inside of the reticular skeleton is provided with the tough polymer, the gas diffusion layer prepared by the modified carbon substrate shows good elasticity, under the larger loading pressure, the gas diffusion layer generates micro deformation, only a few reticular skeletons are crushed and attached to the tough polymer inside, the high-strength reticular skeleton continuously provides support, the microstructure of the air holes and the liquid through holes of the microporous layer is prevented from being damaged, the porosity of the gas diffusion layer is ensured, meanwhile, the few damaged reticular skeletons also enable the internal network structure to gradually become compact, the strength is further increased, and further support is provided for the microporous layer. Macroscopically, the gas diffusion layer prepared by the modified substrate layer shows good strength and toughness under the action of repeatedly loaded loading pressure, the porosity of the gas diffusion layer is ensured, the gas diffusion layer has good ventilation and drainage capabilities, the chemical reaction of the fuel cell is ensured to be carried out smoothly, and higher voltage is shown under the same current density, so that the power density of the pile is improved, and the fuel cell has good performance.
After a cyclic compression experiment, the gas diffusion layer provided by the invention has the advantages that the transverse tensile strength is 13.2-16.1MPa, the longitudinal tensile strength is 8.1-9.8MPa, the strength is high, the porosity is 61.25-70.22%, the porosity reduction rate is 6.91-10.58%, the retention rate is high, the voltage is 0.386-0.412V, the reduction rate is 22.8-25.0%, the reduction range is low, the power density of a fuel cell is high, and the performance is good.
While the preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.
Claims (15)
1. The modified substrate layer is characterized by comprising a carbon substrate layer and a composite gel layer loaded on the carbon substrate layer, wherein the composite gel layer is provided with a net-shaped framework and a polymer filled in the net-shaped framework.
2. The modified substrate layer of claim 1 wherein the composite gel layer loading is 0.01-1 μ g/cm 2 。
3. The modified substrate layer of claim 2 wherein the composite gel layer loading is 0.1-0.5 μ g/cm 2 。
4. The modified substrate of any of claims 1-3 wherein the composite gel layer comprises a polyacrylamide-alginate.
5. The modified substrate of claim 4, wherein the polyacrylamide-alginate comprises at least one of polyacrylamide-sodium alginate, polyacrylamide-potassium alginate, and polyacrylamide-calcium alginate.
6. The modified substrate layer of claim 1 wherein the carbon substrate layer has a hydrophobic coating.
7. A method of preparing a modified substrate layer according to any one of claims 1 to 6, comprising the steps of:
dipping the carbon substrate layer in the composite hydrogel for 20-40min at 20-60 ℃, and then curing to obtain a modified substrate layer; the composite hydrogel is provided with a reticular framework and a polymer filled in the reticular framework.
8. The method of preparing a modified substrate layer of claim 7 wherein the temperature of the dipping process is 35-60 ℃ and the time of the dipping process is 25-35 min.
9. The method of preparing a modified substrate layer of claim 7 wherein the composite hydrogel comprises a polyacrylamide-alginate hydrogel.
10. The method of preparing a modified substrate layer of claim 9, wherein the polyacrylamide-alginate hydrogel is prepared by a method comprising:
mixing alginate, acrylamide, a first cross-linking agent and an initiator, then dripping an accelerator, stirring and curing for 2.5-3.5h to prepare cross-linked gel;
and (3) placing the crosslinked gel in a second crosslinking agent to be soaked for 18-22min for hybridization to obtain the polyacrylamide-alginate hydrogel.
11. The method of preparing a modified substrate layer of claim 10, wherein the alginate comprises at least one of sodium alginate, potassium alginate, and calcium alginate.
12. The method of preparing a modified substrate layer according to any of claims 7-11, further comprising the steps of, before the carbon substrate layer is impregnated with the composite hydrogel:
and (3) soaking the carbon substrate layer in a hydrophobic agent for 25-35min, and drying at 50-70 ℃ for 50-70 min.
13. A gas diffusion layer, comprising:
the modified substrate layer according to any one of claims 1 to 6 or the modified substrate layer obtained by the production method according to any one of claims 7 to 12;
a microporous layer overlying the modified base layer.
14. A membrane electrode comprising the modified substrate layer of any one of claims 1 to 6, or the modified substrate layer produced by the production method of any one of claims 7 to 12, or the gas diffusion layer of claim 13.
15. A fuel cell comprising the modified substrate layer of any one of claims 1 to 6, or the modified substrate layer produced by the production method of any one of claims 7 to 12, or the gas diffusion layer of claim 13, or the membrane electrode of claim 14.
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