CN117374313A - Gas diffusion layer of proton exchange membrane fuel cell and preparation method and application thereof - Google Patents
Gas diffusion layer of proton exchange membrane fuel cell and preparation method and application thereof Download PDFInfo
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- CN117374313A CN117374313A CN202311365355.6A CN202311365355A CN117374313A CN 117374313 A CN117374313 A CN 117374313A CN 202311365355 A CN202311365355 A CN 202311365355A CN 117374313 A CN117374313 A CN 117374313A
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 62
- 239000000446 fuel Substances 0.000 title claims abstract description 51
- 239000012528 membrane Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 87
- 239000011148 porous material Substances 0.000 claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000077 silane Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 238000005507 spraying Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000002002 slurry Substances 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000002270 dispersing agent Substances 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 150000004756 silanes Chemical class 0.000 claims description 16
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- 238000010438 heat treatment Methods 0.000 claims description 6
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- 239000002028 Biomass Substances 0.000 claims description 4
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 235000013312 flour Nutrition 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 125000002577 pseudohalo group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 210000004027 cell Anatomy 0.000 claims 4
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 210000000170 cell membrane Anatomy 0.000 claims 1
- 125000004965 chloroalkyl group Chemical group 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 11
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- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 46
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- 238000005303 weighing Methods 0.000 description 17
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- -1 Polytetrafluoroethylene Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
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- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
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- 238000011010 flushing procedure Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M8/0234—Carbonaceous material
-
- 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]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to a gas diffusion layer of a proton exchange membrane fuel cell, a preparation method and application thereof. The gas diffusion layer of the invention is composed of a macroporous carbon substrate and a microporous layer. The microporous layer adopts a pore-forming agent to form a porous structure, which is beneficial to the water vapor transmission in the fuel cell. The invention adopts SiO with different diameters 2 Preparing a series of porous carbon materials with uniform pore diameters as a hard template, grafting hydrophobic silane onto the surface of the porous carbon by adopting a chemical grafting method, and finally uniformly spraying or scraping the modified materials onto a carbon paper substrate by an ultrasonic spraying or scraping device to form a microporous layer, wherein the pore diameters of the microporous layer are uniformly distributed and have good hydrophobicity. The inventionThe porous carbon materials with different apertures are sprayed or scraped in a layering way, the directional gradient aperture can be formed through simple operation, compared with the single aperture, the performance of layered samples is obviously improved, the discharge of cathode product water is facilitated, the water vapor transmission can be effectively enhanced, and the battery performance is improved.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a gas diffusion layer of a proton exchange membrane fuel cell, and a preparation method and application thereof.
Background
One of the core components of a Proton Exchange Membrane Fuel Cell (PEMFC) is a membrane electrode, the composition of which includes a Proton Exchange Membrane (PEM), a Catalytic Layer (CL), and a Gas Diffusion Layer (GDL) with a microporous layer (MPL). The gas diffusion layer is positioned between the catalytic layer and the gas flow field, plays a role in supporting the catalytic layer and collecting current, and is also a necessary transmission channel for reaction gas and product water. The method has the specific effects of uniformly distributing and transmitting the reaction gas to the surface of the catalyst layer and simultaneously discharging liquid water of a reaction product. In the operation process of the PEMFC, on one hand, a certain amount of water is kept to improve the wettability of the proton exchange membrane and reduce the ohmic overpotential of the membrane; on the other hand, excessive liquid water content can cause liquid water to occupy the pores of the gas diffusion layer and cover the surface of the catalyst, so that the transmission resistance of the reaction gas is greatly increased, the phenomenon of flooding of the electrode is caused, and serious concentration polarization loss is caused. To improve the mass transfer of the reaction gas and liquid water in the GDL, carbon paper or cloth is usually subjected to hydrophobization treatment to construct a hydrophobic gas phase channel, and a microporous layer (MPL) made of conductive carbon black and Polytetrafluoroethylene (PTFE) by physical mixing is added between the carbon paper or cloth and the catalytic layer to improve the water vapor transport in the PEMFC. Pore formers are generally used to control the pore size of MPL, such as pyrolysis (NH) 4 ) 2 CO 3 And (NH) 4 )C 2 O 4 Dissolved CaCO 3 、Li 2 CO 3 NaCl and NH 4 NO 3 And the like, the pore-forming agents are easy to operate when in use, can form through holes and are easy to remove.
The traditional method adopts porous carbon powder and PTFE to be physically mixed to prepare MPL, which is easy to influence the pore size distribution and even leads to the formation of partial blocking holes. Meanwhile, PTFE needs to be melted by heat treatment at about 350 ℃, so that the production cost is increased to a certain extent, and the water resistance is also improved. Research shows that the water management capability of the fuel cell can be improved by using the pore-forming agent to prepare the MPL with graded porosity and multi-pore distribution, meanwhile, under the condition of certain hydrophobicity, the directional gradient pore diameter can additionally generate driving force transferred from small pores to large pores, the product water discharge speed is accelerated, and the cell performance under high current density is obviously improved. Therefore, the research and development of a novel microporous layer preparation process has important significance for improving stability and mass transfer efficiency.
Disclosure of Invention
In order to solve the technical problems, the invention provides a gas diffusion layer of a proton exchange membrane fuel cell and a preparation method and application thereof, in particular to a gradient pore microporous layer for the proton exchange membrane fuel cell and a preparation method and application thereof. The invention takes sucrose, glucose, fructose, flour, biomass, resin and the like as carbon sources, adopts SiO 2 A series of porous carbon materials are prepared by a template method, molecular-level hydrophobic agents are uniformly grafted on the upper surface of the materials by a chemical grafting method, and microporous layers in a gas diffusion layer are prepared by layered spraying or knife coating on a carbon substrate according to a certain sequence.
The invention is realized by the following technical scheme:
the first object of the invention is to provide a gas diffusion layer of a proton exchange membrane fuel cell, which comprises a substrate, a silane modified porous carbon material and a binder; the silane modified porous carbon material is composed of silane modified porous carbon materials with different pore diameters, and the silane modified porous carbon materials are sequentially coated on a substrate in a layering manner according to the order of pore diameters from large to small. The silane modified porous carbon material has controllable and uniform pore size and strong water-flushing resistance.
In one embodiment of the invention, the pore size is 20nm-400nm; for example, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm.
In one embodiment of the invention, the silane modified porous carbon material is prepared by the following method:
(1) SiO is adopted 2 Preparing a porous carbon material by a template method;
(2) Hydroxylation treatment is carried out on the surface of the obtained porous carbon material, so that the carbon material with hydroxyl on the surface is obtained;
(3) And mixing the obtained carbon material with the hydroxyl on the surface, the dispersing agent and the silane, and heating and stirring to obtain the silane modified porous carbon material.
In one embodiment of the present invention, in step (1), the carbon source for preparing the porous carbon material is selected from one or more of sucrose, glucose, fructose, flour, biomass and resin.
In one embodiment of the present invention, in the step (2), the hydroxylation method is to perform hydroxylation treatment on the material by using a Fenton reagent, specifically, to treat the porous carbon material with a hydrogen peroxide solution and an iron salt with a certain concentration, so as to obtain a hydroxylated carbon material. Wherein, the proportion of ferric salt, hydrogen peroxide and porous carbon material is (0.5-1) g:30mL: (0.1-0.2) g. Or the hydroxylation treatment method is to treat the carbon material with a strong oxidant, wherein the typical strong oxidant is concentrated nitric acid or potassium permanganate; specifically, 1g of carbon material is dispersed in (50-150) mL 65% nitric acid solution, reflux stirring is carried out for 4-8 h at 80 ℃, deionized water is used for washing for multiple times, and the carbon material with hydroxyl on the surface is obtained after drying.
In one embodiment of the present invention, in step (3), the silane is selected from one or more of vinyl-based silanes, chlorohydrocarbyl-based silanes, aminoalkyl-based silanes, epoxyhydrocarbyl-based silanes, methacryloxyalkyl-based silanes, sulfur-containing hydrocarbyl-based silanes, pseudohalogen-based silanes, and alkane-based silanes.
In one embodiment of the present invention, in step (3), the dispersant is selected from one or more of isopropanol, ethanol, and deionized water; the metering ratio of the carbon material with hydroxyl on the surface, the silane and the dispersing agent is 1g: (5-10) mL:50mL.
In one embodiment of the invention, the substrate is selected from carbon paper and/or carbon cloth.
In one embodiment of the invention, the binder is selected from one or more of Nafion solution, PTFE, and PVDF.
The second object of the present invention is to provide a method for preparing a gas diffusion layer of a proton exchange membrane fuel cell, comprising the steps of:
respectively mixing silane modified porous carbon materials with different pore diameters with a dispersing agent and a binder to obtain microporous layer slurry with different pore diameters;
and sequentially spraying or knife-coating the obtained microporous layer slurry with different pore diameters on a substrate according to the sequence from large pore diameters to small pore diameters, and drying to obtain the gas diffusion layer of the proton exchange membrane fuel cell.
In one embodiment of the present invention, the dispersant is selected from one or more of isopropanol, ethanol and deionized water; the ratio of the silane modified porous carbon material, the dispersing agent and the adhesive is (0.1-0.2) g:10mL: (0.1-0.2) mL.
In one embodiment of the invention, the microporous layer carbon material is present on the substrate at a loading of 0.5mg/cm 2 -2.0mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The mass of the hydrophobe in the microporous layer slurry accounts for 1-20% of the carbon material.
The third object of the invention is to provide the application of the gas diffusion layer of the proton exchange membrane fuel cell in preparing the membrane electrode of the fuel cell.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the gas diffusion layer of the invention is composed of a macroporous carbon substrate and a microporous layer. Microporous layers typically employ pore formers to form porous structures that have been shown to facilitate moisture transport in fuel cells. The invention firstly adopts SiO with different diameters 2 Preparing a series of porous carbon materials with uniform pore diameters as a hard template; the pore size of the porous carbon material prepared by the method is uniform and controllable, and the combination of different pore sizes is carried out, so that the influence of the pore size on the performance of the fuel cell can be quantitatively analyzed.
2. According to the method, the hydrophobic silane is grafted onto the surface of the porous carbon by adopting a chemical grafting method, and finally, the modified material is uniformly sprayed or knife-coated on the carbon paper substrate by using an ultrasonic spraying or knife-coating instrument to form a microporous layer.
3. According to the invention, porous carbon materials with different apertures are sprayed or scraped in a layered manner, and the directional gradient aperture can be formed through simple operation, so that the performance of a directional gradient aperture sample is remarkably improved compared with that of a single aperture. Research shows that the directional gradient pore diameter is more favorable for the discharge of cathode product water, can effectively enhance the water vapor transmission and improve the battery performance.
4. The preparation method can avoid the phenomenon of blocking holes similar to the traditional physical mixing and coating of PTFE.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings, in which
FIG. 1 is a schematic cross-sectional view of embodiment 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the porous carbon material of comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5, comparative example 6; wherein a is 20nm pore size porous carbon (comparative example 1), b is 60nm pore size porous carbon (comparative example 2), c is 100nm pore size porous carbon (comparative example 3), d is 200nm pore size porous carbon (comparative example 4), e is 400nm pore size porous carbon (comparative example 5), and f is porous carbon of a mixture of three pore sizes of 100nm,200nm and 400nm (comparative example 6);
FIG. 3 is a scanning electron microscope image of comparative example 5 before and after chemical modification of the present invention; wherein a is a porous carbon that is not hydrophobically modified; b is porous carbon modified by hydrophobic property;
FIG. 4 is an infrared comparison of porous carbon before and after chemical modification of comparative example 5 of the present invention;
FIG. 5 is a graph showing the contact angle of microporous layers prepared before and after chemical modification according to comparative example 5 of the present invention; wherein a and b are respectively the contact angle test of the non-hydrophobic modified material for 0 seconds and 30 seconds; c and d are respectively the contact angle test of the hydrophobically modified material for 0 seconds and 30 seconds;
FIG. 6 is a graph showing the comparison of the performance curves of a fuel cell assembled with a cathode gas diffusion layer prepared in example 1 of the present invention and a fuel cell assembled with a cathode gas diffusion layer prepared in comparative example 1;
FIG. 7 is a graph showing the comparison of the performance curves of a fuel cell assembled with a cathode gas diffusion layer prepared in example 2 according to the present invention and a fuel cell assembled with a cathode gas diffusion layer prepared in comparative example 2;
FIG. 8 is a graph showing the comparison of the performance curves of a fuel cell assembled with a cathode gas diffusion layer prepared in example 3 according to the present invention and a fuel cell assembled with a cathode gas diffusion layer prepared in comparative example 3;
FIG. 9 is a graph showing the comparison of the performance curves of a fuel cell assembled with a cathode gas diffusion layer prepared in example 3 according to the present invention and a fuel cell assembled with a cathode gas diffusion layer prepared in comparative example 4;
FIG. 10 is a graph showing the comparison of the performance curves of a fuel cell assembled with a cathode gas diffusion layer prepared in example 3 according to the present invention and a fuel cell assembled with a cathode gas diffusion layer prepared in comparative example 5;
FIG. 11 is a graph showing the comparison of the performance curves of a fuel cell assembled with a cathode gas diffusion layer prepared in example 3 according to the present invention and a fuel cell assembled with a cathode gas diffusion layer prepared in comparative example 6;
FIG. 12 is a graph showing the comparison of the performance curves of a fuel cell assembled with a cathode gas diffusion layer prepared in example 2 of the present invention and a fuel cell assembled with a cathode gas diffusion layer prepared in comparative example 7;
fig. 13 is a graph showing comparison of performance curves of assembled fuel cells of cathode gas diffusion layers prepared in examples 1, 2, 3, and 4 according to the present invention.
Detailed Description
The gas diffusion layer of the proton exchange membrane fuel cell plays roles of transmitting reaction gas, conducting heat and mechanically supporting membrane electrodes and timely discharging product water. Therefore, the method has important significance for exploring the proper pore size in water management. The invention adopts SiO 2 A series of porous carbon materials with uniform aperture are prepared by a template method, meanwhile, a hydrophobic agent is grafted on the surface of the carbon materials by a chemical grafting method, and then the carbon materials with different aperture hydrophobic treatments are sprayed or scraped on a carbon substrate according to a certain sequence to be compounded into a microporous layer in a gas diffusion layer. The porous carbon material prepared by the method has uniform pore size, and is beneficial to qualitatively analyzing the influence of directional gradient pore size distribution on the performance of the fuel cell.
As an example, the method for preparing the gas diffusion layer of the proton exchange membrane fuel cell provided by the invention comprises the following steps:
1) SiO is adopted 2 Hard template method using glucose, sucrose, fructose, biomass, flour, resin, etcOne or more of deionized water and ethanol are used as dispersing agents, and SiO is used as a carbon source 2 The mass ratio of the carbon source to the dispersing agent is (0.5-2) 1:50, stirring and ultrasonic treatment is carried out for a plurality of hours, then the mixture is placed in a blast oven at 60 ℃ for slow drying for a plurality of hours, and then the mixture is calcined at a high temperature of 800 ℃ to carbonize the mixture, and SiO with different diameters is changed 2 Preparing a series of porous carbon materials;
2)SiO 2 the method is characterized in that the traditional HF etching method is adopted, HF and deionized water are used as dispersing agents, the mass ratio of the carbon materials to the dispersing agents is (0.1-0.5): 50, stirring is carried out for a plurality of hours, and centrifugal washing is carried out for a plurality of times, so that the porous carbon material with uniform aperture is obtained.
3) Hydroxylation treatment is carried out on the surface of the porous carbon material, so that the surface of the porous carbon material has functional groups such as-OH and the like. The dispersing agent is one or more of deionized water, ethanol, methanol or isopropanol, and FeCl 2 ·4H 2 O or FeSO 4 ·6H 2 O, etc. are used as catalysts, the pH of the dispersant is adjusted to 3-4 by using hydrochloric acid solution with the concentration of 0.1M, and the mass fraction of H is 30wt% 2 O 2 Diluting the solution according to the proportion of 1:3, dropwise adding the solution, stirring at room temperature, dropwise adding the solution for 2-3 h, and carrying out suction filtration, washing and drying to obtain the porous carbon material with a large number of functional groups such as hydroxyl groups on the surface. The mass ratio of the carbon powder to the dispersant to the catalyst is (0.1-0.5), and the mass ratio of the carbon powder to the dispersant is (20-50), and the mass ratio of the catalyst to the catalyst is (0.5-1).
4) Dispersing the hydroxylated carbon material in a mixed solution of deionized water and ethanol or ethylene glycol or isopropanol, wherein the mass ratio of the material to the water to the alcohol is (0.1-0.5) 5 (25-50), and adding acetic acid or 0.1M hydrochloric acid solution to adjust the pH value of the solution to 4-5;
5) Adding silane into the solution, wherein the mass ratio of the carbon material to the silane is 1 (1-5), controlling the water bath temperature at 50-70 ℃, setting the speed at 300rpm, mechanically stirring for 1-6 h, centrifugally filtering with water and ethanol, washing for several times, and drying the obtained silane modified porous carbon material in a 60 ℃ oven for standby;
6) Dispersing the prepared silane modified porous carbon material in one or more mixed solutions of isopropanol, ethanol or water, and simultaneously adding a binder Nafion, wherein the Nafion content accounts for 1-20wt% of the carbon material, and performing ultrasonic dispersion for 2-8 h to form microporous layer slurry;
7) The microporous layer slurry is compounded on the carbon paper substrate in a lamination compounding mode by adopting a spraying or knife coating method, dried and weighed, and then the steps are repeated until the carbon loading amount reaches 0.5mg/cm 2 -2.0mg/cm 2 And finally obtaining the gas diffusion layer of the proton exchange membrane fuel cell.
8) The testing method comprises the following steps: the prepared gas diffusion layer was assembled as a cathode gas diffusion layer with a commercial membrane electrode (Pt content of 20 wt%) and a commercial anode gas diffusion layer to a fuel cell for testing. The temperature of the battery is 80 ℃, the relative humidity is 40 percent, and H 2 And air stoichiometric ratio of 1.5:3, back pressure of 1atm, test area of 25cm 2 . The test used was a U.S. fuel cell test system (Scribner Associates, inc,850Fuel Cell Test System).
In order to facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely provided to aid in understanding the invention and are not intended to limit the invention to the scope of the examples. The raw materials involved in the invention are conventional products for batteries, and the specific preparation operation and the testing method are conventional methods.
All the cells in the following examples and comparative examples were identical in the remaining constituent parts except for the cathode gas diffusion layer.
Spherical SiO of uniform diameter 2 Referring to the ready-made synthesis scheme, the specific procedure is as follows:
20nm SiO 2 :14.5mL dodecane, 139mL deionized water and 0.146g lysine are fully and uniformly stirred, then 11.5mL tetraethyl orthosilicate (TEOS) is added, heating and stirring are carried out at 60 ℃ for 24 hours, then the mixture is put into a 100 ℃ oven for standing for 20 hours, then the mixture is put into a tube furnace, heated to 600 ℃ at a speed of 2 ℃/min and annealed for 3 hours in an air atmosphere.
60nm SiO 2 :100mL of ethanol, 10mL of deionized water and 2.74mL of ammonia water are fully and uniformly stirred, then 2.5mL of tetraethyl orthosilicate (TEOS) is added, stirring is carried out for 4 hours at room temperature and 300rpm, high-speed centrifugation is carried out, then deionized water is used for washing for a plurality of times, and drying is carried out in a blast oven at 60 ℃ for standby.
100nm SiO 2 :25mL of ethanol, 25mL of deionized water and 4mL of ammonia water are fully and uniformly stirred, then 1mL of tetraethyl orthosilicate (TEOS) is added, stirring is carried out at 300rpm for 7 hours at room temperature, high-speed centrifugation is carried out, then deionized water is used for washing for a plurality of times, and drying is carried out in a blast oven at 60 ℃ for standby.
200nm SiO 2 :50mL of ethanol and 4mL of ammonia water are fully and uniformly stirred, then 1mL of tetraethyl orthosilicate is added, stirring is carried out at room temperature and 300rpm for 7h, high-speed centrifugation is carried out, then deionized water is used for washing for a plurality of times, and drying is carried out in a blast oven at 60 ℃ for standby.
400nm SiO 2 :65mL of ethanol, 14.7mL of deionized water and 80mL of ammonia water are fully and uniformly stirred, 6.94mL of tetraethyl orthosilicate is added, stirring is carried out at 300rpm at room temperature for 4 hours, high-speed centrifugation is carried out, deionized water is used for washing for a plurality of times, and the mixture is dried in a blast oven at 60 ℃ for standby.
(a) Initial porous material synthesis:
1.25g of SiO was weighed out 2 (one of 20nm,60nm,100nm,200nm,400nm diameter), 1g glucose, dispersed in 30mL deionized water and 10mL ethanol, sonicated for 1h, stirred for 1h, and alternated several times until SiO 2 Is fully dispersed in the solution. Standing for 24h, transferring to a 60 ℃ oven, and slowly drying the dispersing agent until forming tightly packed cake-shaped glucose and SiO 2 And (3) a mixture. Then, the obtained product was annealed at a heating rate of 5 ℃ per minute for 2 hours in a nitrogen atmosphere in a 800 ℃ tube furnace. Dispersing carbonized materials in 20mL of HF and 30mL of deionized water, stirring at a constant speed for more than 6 hours, finally, centrifugally washing with water and ethanol for multiple times until the solution is neutral, drying in a 60 ℃ oven for standby to obtain initial porous carbon materials, wherein a scanning electron microscope diagram corresponding to each pore diameter material is shown as a figure 2, and the pore diameter distribution of the initial porous carbon materials prepared by the invention is uniform and controllable as can be seen from the figure 2.
(b) Preparing a hydroxylated porous carbon material:
0.2g of the initial porous carbon material was weighed and dispersed in 40mL of deionized water, the pH was adjusted to about 3.5 with 0.1M hydrochloric acid solution, stirred and heated to 35 ℃. Subsequently, 0.98g FeCl was weighed out 2 ·4H 2 O is added to the dispersion, surpassingThe mixture was completely dissolved by applying sound for 30min. A 30wt% hydrogen peroxide solution was diluted with deionized water at a volume ratio of 1:3. 100mL of diluted hydrogen peroxide solution was added dropwise to the dispersion via a separating funnel, and reacted for 2 hours. The reaction product was washed by filtration with 0.1M hydrochloric acid solution to remove iron ions remaining in the product, and then washed to neutrality using a large amount of deionized water. Finally, the obtained hydroxylated carbon material is placed in a vacuum oven at 40 ℃ and dried for 24 hours.
(c) Preparing a silane modified porous carbon material:
0.2g of the hydroxylated carbon material was weighed and dispersed in a mixed solution of 45mL of ethanol and 5mL of deionized water, and sonicated for 30min. Adjusting the pH to about 4.5 by using 0.1M hydrochloric acid solution, adding 1mL of perfluoro-sunflower-base trimethoxy silane, stirring for 4 hours in a water bath at 60 ℃, filtering and washing the product with water and ethanol for multiple times, and then putting into a 60 ℃ oven for drying to obtain the silane modified porous carbon material. The scanning electron microscope diagram of the carbon material is shown in fig. 3, and as can be seen from fig. 3, the chemical grafting hydrophobic modification well retains the initial structure. The Fourier infrared spectrum (FTIR) results of the carbon material are shown in FIG. 4, and it can be seen from FIG. 4 that the silane modified porous carbon material is at 1239.69cm -1 And 1208.05cm -1 The peak at 1150.03cm is a fluorine-containing functional group -1 The peak of (C) is Si-O-C bond, 1068.28cm -1 And 964.98cm -1 These results indicate successful grafting of the silane onto the porous carbon material.
(d) Preparing microporous layer slurry, and spraying or knife coating:
0.1g of the silane-modified porous carbon material and 0.1g of Nafion solution (5 wt%) were weighed and dispersed in 10mL of isopropanol solution, and ultrasonic dispersion was performed for a total of 8 hours to form a uniform microporous layer slurry. Spraying or knife coating the microporous layer slurry on the carbon paper substrate by using an ultrasonic spraying or knife coating instrument, and drying at 80 ℃ to obtain the gas diffusion layer, wherein the loading amount of the porous carbon material is 1.0mg/cm 2 As shown in fig. 5, the contact angle of the obtained gas diffusion layer was 148 °, and the gas diffusion layer exhibited superhydrophobic characteristics, whereas the contact angle without surface hydrophobic treatment was only about 85 °, and after 30 seconds, the contact angle was reduced to 0 °.
Example 1
And (3) weighing hydrophobic porous carbon materials with the same mass and pore diameters of 20nm,60nm and 100nm, preparing slurry according to the steps, and sequentially spraying or scraping the slurry with the pore diameters of 100nm,60nm and 20nm on the surface of the carbon paper to obtain directional gradient graded pores with the pore diameters from a macroporous diffusion substrate to a catalytic layer from large to small. Accurately weighing and calculating the carbon load to reach 1mg/cm 2 The cross section of the sample is clearly shown in fig. 1, wherein the actual thickness of each microporous layer is about several micrometers, and the actual thickness of the carbon paper is about 190 micrometers. The prepared gas diffusion layer was assembled as a cathode gas diffusion layer with a commercial membrane electrode (Pt content of 20 wt%) and a commercial anode gas diffusion layer to a fuel cell for testing. The temperature of the battery is 80 ℃, the relative humidity is 40 percent, and H 2 And air stoichiometric ratio of 1.5:3, back pressure of 1atm, test area of 25cm 2 . The test used was a U.S. fuel cell test system (Scribner Associates, inc,850Fuel Cell Test System). As shown in FIG. 6, the peak output power of the battery was 1054.59mW/cm 2 。
Example 2
The hydrophobic porous carbon materials with the same mass and pore diameters of 60nm,100nm and 200nm are weighed, slurries are prepared according to the steps, and the slurries of 200nm,100nm and 60nm are sequentially sprayed or scraped on the surface of the carbon paper, so that directional gradient graded pores with the pore diameters from a macroporous diffusion substrate to a catalytic layer from large to small are obtained. The subsequent steps were consistent with example 1, as shown in FIG. 7, with a peak battery output of 1288.95mW/cm 2 。
Example 3
The hydrophobic porous carbon materials with the same mass and the pore diameters of 100nm,200nm and 400nm are weighed, slurries are prepared according to the steps, and the slurries with the pore diameters of 400nm,200nm and 100nm are sequentially sprayed or scraped on the surface of the carbon paper, so that directional gradient graded pores with the pore diameters from a macroporous diffusion substrate to a catalytic layer from large to small are obtained. The subsequent steps were consistent with example 1, as shown in FIG. 8, with a peak battery output of 1242.69mW/cm 2 。
Example 4
The same mass is weighed, and the pore diameters are respectively 20nm,60nm and 1The hydrophobic porous carbon material with the aperture of 400nm,200nm and 400nm is prepared by respectively preparing the slurry according to the steps, and the slurry with the aperture of 400nm,200nm,100nm,60nm and 20nm is sequentially sprayed or scraped on the surface of the carbon paper, so that the directional gradient graded holes with the aperture from the macroporous diffusion substrate to the catalytic layer from large to small are obtained. The subsequent steps were consistent with example 1, as shown in FIG. 13, with a peak battery output of 1113.18mW/cm 2 。
Comparative example 1
Weighing a hydrophobic porous carbon material with the pore diameter of 20nm, preparing slurry according to the steps, spraying or scraping the slurry with the pore diameter of 20nm on the surface of carbon paper, accurately weighing and calculating the carbon load to reach 1mg/cm 2 . The test conditions were identical to those of example 1. As shown in FIG. 6, the peak output power of the battery was 980.93mW/cm 2 。
Comparative example 2
Weighing a hydrophobic porous carbon material with the pore diameter of 60nm, preparing slurry according to the steps, spraying or scraping the slurry with the pore diameter of 60nm on the surface of the carbon paper, accurately weighing and calculating the carbon load to reach 1mg/cm 2 . The test conditions were identical to those of example 1. As shown in FIG. 7, the peak output power of the battery was 981.06mW/cm 2 。
Comparative example 3
Weighing a hydrophobized porous carbon material with the aperture of 100nm, preparing slurry according to the steps, spraying or scraping the slurry with the aperture of 100nm on the surface of carbon paper, accurately weighing and calculating the carbon load to reach 1mg/cm 2 . The test conditions were identical to those of example 1. As shown in FIG. 8, the peak output power of the battery was 1070.45mW/cm 2 。
Comparative example 4
Weighing a hydrophobic porous carbon material with the aperture of 200nm, preparing slurry according to the steps, spraying or scraping the slurry with the aperture of 200nm on the surface of carbon paper, accurately weighing and calculating the carbon load to reach 1mg/cm 2 . The test conditions were identical to those of example 1. As shown in FIG. 9, the peak output power of the battery was 1124.81mW/cm 2 。
Comparative example 5
Weighing hydrophobic porous carbon material with aperture of 400nm, preparing slurry according to the steps, spraying or knife coating 400nm slurry on the surface of carbon paper,accurately weighing and calculating the carbon load to reach 1mg/cm 2 . The test conditions were identical to those of example 1. As shown in FIG. 10, the peak output power of the battery was 1071.56mW/cm 2 。
Comparative example 6
Weighing 0.4g of 100nm SiO 2 ，0.4g 200nm SiO 2 ，0.45g 400nm SiO 2 1g glucose, adding 30mL deionized water and 10mL ethanol, performing ultrasonic treatment for 1h, stirring for 1h, and alternately repeating for several times until SiO 2 Is fully dispersed in the solution. Standing for 24h, transferring to a 60 ℃ oven, and slowly drying the dispersing agent until thinner and hard cake-shaped glucose and SiO are formed 2 And (3) a mixture. Then, the obtained product was annealed at a heating rate of 5 ℃ per minute for 2 hours in a nitrogen atmosphere in a 800 ℃ tube furnace. Dispersing the carbonized material in 20mL of HF and 30mL of deionized water, stirring at a constant speed for more than 6 hours, and finally, centrifugally washing with ethanol and water for multiple times until the solution is neutral, and drying in a 60 ℃ oven for standby, wherein a scanning electron microscope chart is shown in figure 2. Hydroxylation, hydrophobization and spraying or blade coating operations are in accordance with the above.
Weighing 100nm,200nm and 400nm pore size mixed hydrophobic porous carbon material, preparing slurry according to the steps, spraying or knife coating the slurry on the surface of carbon paper, accurately weighing and calculating the carbon load to reach 1mg/cm 2 . The test conditions were identical to those of example 1. As shown in FIG. 11, the peak output power of the battery was 1171.77mW/cm 2 。
Comparative example 7
And (3) weighing the hydrophobic porous carbon materials with the same mass and pore diameters of 20nm,60nm and 100nm, preparing slurry according to the steps, and sequentially spraying or scraping the slurry with the pore diameters of 20nm,60nm and 100nm on the surface of the carbon paper to obtain directional gradient graded pores with the pore diameters from a macroporous diffusion substrate to a catalytic layer from small to large. Accurately weighing and calculating the carbon load to reach 1mg/cm 2 . The test conditions were identical to those of example 1. As shown in FIG. 12, the peak output power of the battery was 969.78mW/cm 2 。
The invention adopts SiO with controllable diameter as the material 2 The porous carbon material with uniform aperture is successfully prepared by sacrificing the template, and the chemical grafting method is adopted to graft hydrophobic materialThe aqueous silane substance achieves the super-hydrophobic effect, well maintains the original pore structure, combines the material with the carbon substrate through ultrasonic spraying or knife coating, and simultaneously achieves the purpose of directional gradient through sequentially spraying or knife coating materials with different pore diameters, thereby successfully enhancing the battery performance.
The invention belongs to the technical field of fuel cells, and particularly discloses a preparation method of a microporous layer in a gas diffusion layer and application of the microporous layer in a proton exchange membrane fuel cell. Using SiO 2 The porous carbon material prepared by the template method is prepared by grafting hydrophobic silane on the surface by a chemical grafting method, preparing the silane modified porous carbon material into slurry, and compositing the slurry on a carbon paper substrate by utilizing an ultrasonic spraying or knife coating mode to form the microporous layer for the fuel cell. The fuel cell gas diffusion layer disclosed by the invention has the following advantages: siO is adopted 2 A series of porous carbon materials with uniform pore size are prepared by a template method, and hydrophobic silane is grafted on the surface of the carbon materials by a chemical grafting method to achieve the effect of stabilizing the hydrophobicity, so that a more stable microporous layer is constructed. The gas diffusion layer prepared by the method can effectively promote the water vapor transmission of a three-phase interface, improves the output power of the fuel cell, and opens up a promising approach for explaining the performance influence of the directional gradient aperture on the fuel cell and the water vapor transmission mechanism.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A gas diffusion layer of a proton exchange membrane fuel cell, comprising a substrate, a silane modified porous carbon material and a binder; the silane modified porous carbon material is sequentially coated on the substrate layer by layer according to the sequence of the pore diameters from large to small.
2. The gas diffusion layer according to claim 1, wherein the pore size is 20nm-400nm.
3. The gas diffusion layer of claim 1, wherein the silane modified porous carbon material is prepared by:
(1) SiO is adopted 2 Preparing a porous carbon material by a template method;
(2) Hydroxylation treatment is carried out on the surface of the obtained porous carbon material, so that the carbon material with hydroxyl on the surface is obtained;
(3) And mixing the obtained carbon material with the hydroxyl on the surface, the dispersing agent and the silane, and heating and stirring to obtain the silane modified porous carbon material.
4. A gas diffusion layer according to claim 3, wherein in step (1), the carbon source from which the porous carbon material is made is selected from one or more of sucrose, glucose, fructose, flour, biomass and resins.
5. The gas diffusion layer of claim 1, wherein in step (3), the silane is selected from one or more of vinyl-based silanes, chloroalkyl-based silanes, aminoalkyl-based silanes, epoxyalkyl-based silanes, methacryloxyalkyl-based silanes, sulfur-containing alkyl-based silanes, pseudohalogen-based silanes, and alkane-based silanes.
6. The gas diffusion layer of claim 1, wherein in step (3), the dispersant is selected from one or more of isopropanol, ethanol, and deionized water; the metering ratio of the carbon material with hydroxyl on the surface, the silane and the dispersing agent is 1g: (5-10) mL:50mL.
7. The gas diffusion layer according to claim 1, wherein the substrate is selected from carbon paper and/or carbon cloth.
8. A method for preparing a gas diffusion layer of a proton exchange membrane fuel cell, comprising the steps of:
respectively mixing silane modified porous carbon materials with different pore diameters with a dispersing agent and a binder to obtain microporous layer slurry with different pore diameters;
and sequentially spraying or knife-coating the obtained microporous layer slurry with different pore diameters on a substrate according to the sequence from large pore diameters to small pore diameters, and drying to obtain the gas diffusion layer of the proton exchange membrane fuel cell.
9. The method of claim 8, wherein the dispersant is selected from one or more of isopropanol, ethanol, and deionized water; the ratio of the silane modified porous carbon material, the dispersing agent and the adhesive is (0.1-0.2) g:10mL: (0.1-0.2) mL.
10. Use of a gas diffusion layer of a proton exchange membrane fuel cell according to any one of claims 1 to 7 for the preparation of a fuel cell membrane electrode.
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