CN111009666A - A kind of preparation method of double-layer microporous layer type gas diffusion layer - Google Patents
A kind of preparation method of double-layer microporous layer type gas diffusion layer Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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- 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]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention belongs to the technical field of gas diffusion layer preparation, and particularly relates to a preparation method of a double-layer microporous layer type gas diffusion layer, which comprises three steps of hydrophobization treatment, slurry preparation and double-layer microporous layer preparation, wherein a double-layer microporous layer structure with gradient changed pore diameter is prepared by adding a pore-forming agent, the pore-forming agent is added into a microporous layer close to a supporting layer to improve the porosity and change the pore diameter structure, and the microporous layer close to the catalytic layer side is prepared by adopting carbon black and PTFE (polytetrafluoroethylene), and has the following advantages that: (1) compared with the conventional gas diffusion layer, the current density and the power density are higher, and the performance of the prepared fuel cell is more stable; (2) the preparation process is relatively simple, the cost is low, and the preparation method is suitable for large-scale production; (3) the repeatability is good, the preparation process of the microporous layer with the gradient aperture can be repeated, so that the repeatability of the performance of the fuel cell is higher, and the water management capability of the fuel cell is improved.
Description
The technical field is as follows:
the invention belongs to the technical field of gas diffusion layer preparation, and particularly relates to a preparation method of a double-layer microporous layer type gas diffusion layer.
Background art:
proton Exchange Membrane Fuel Cells (PEMFC) can convert chemical energy in fuel directly into electric energy, and are energy conversion devices, such as fuel cell, and fuel cell2Is fuel, air or O2The oxidant is not limited by Carnot cycle, has higher efficiency and lower pollution emission, and the development of new energy automobiles is more and more concerned at present. Meanwhile, the fuel cell has obvious popularization in the fields of mobile power supplies, power generation and the like, and has wide application prospect. A Membrane Electrode Assembly (MEA) is a core component of a fuel cell system, as shown in fig. 1, and includes a Proton Exchange Membrane (PEM), a Catalyst Layer (CL), and a Gas Diffusion Layer (GDL). Wherein the Gas Diffusion Layer (GDL) functions to support the catalyst layer, collect current, and provide an electron channel, a gas channel, and a water discharge channel for electrochemical reaction, and has a structure as shown in fig. 2, the Support Layer (SL) is connected with the gas flow channel, the support layer is required to have good conductivity, enough mechanical strength and a certain water vapor management function, the commonly used material of the support layer is commercial carbon paper or carbon cloth, the aperture of more than 80% of holes in the support layer is more than 20 microns, the thickness is about 100 plus-300 microns, a microporous layer (MPL) above the support layer is connected with the catalyst layer, the microporous layer (MPL) is generally prepared from conductive material carbon powder and hydrophobic agent PTFE, the aperture is generally tens of nanometers to hundreds of nanometers, the thickness is 10-100 microns, the microporous layer (MPL) has certain water management capability, the surface is smooth, and the contact resistance between the catalyst layer and the support layer can be reduced.
The microporous layer of the Gas Diffusion Layer (GDL) plays an important role in improving the water management capability and performance of the fuel cell. Chinese patent 201710573636.9 discloses a microporous layer of gas diffusion layer of proton exchange membrane fuel cell and its preparation method, coating or spraying organic solvent containing organic siloxane and carbon nano material on the surface of support layer after hydrophobic treatment, forming the microporous layer of gas diffusion layer of proton exchange membrane fuel cell by microporous layer interface micro-nano structure and coating layer; wherein, the proportion of the organic siloxane to the carbon nano material is 10 wt% -100 wt%, which shows that the gas diffusion layer coated with the microporous layer at one side close to the catalytic layer can effectively improve the water management capability of the fuel cell, thereby improving the performance of the cell; chinese patent 201910373844.3 discloses a method for preparing a gas diffusion layer of a proton exchange membrane fuel cell oriented to high current density, which comprises the steps of firstly carrying out hydrophobic and drying treatment on a substrate layer, then preparing slurry by utilizing carbon powder, a solvent, a hydrophobic agent and a pore-forming agent, then uniformly attaching the slurry on the substrate layer by adopting a blade coating method to reach a certain loading capacity, and finally drying and sintering to obtain the gas diffusion layer; based on the addition of the pore-forming agent, a plurality of cracks are formed on the surface of the microporous layer of the obtained gas diffusion layer, so that gas and water can be effectively ensured to permeate, the water management capability of the gas diffusion layer is improved, the concentration polarization of the membrane electrode under high current density is reduced, and the performance of the proton exchange membrane fuel cell is improved. However, the microporous layer in the prior art generally has unreasonable pore structure, and the research on the pore size is relatively less. Therefore, the method has important significance in exploring a new structure and a preparation process method aiming at the aperture of the gas diffusion layer to accelerate the electrochemical reaction process, improve the output current density and improve the water management capacity of the fuel cell under high power density.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and develops and designs a preparation method of a double-layer microporous layer type gas diffusion layer so as to improve the water management capability of a fuel cell.
In order to achieve the above object, the process of the preparation method of the double-layer microporous layer gas diffusion layer according to the present invention comprises three steps of hydrophobization, slurry preparation and double-layer microporous layer preparation:
(one) hydrophobization treatment: carrying out combing hydration treatment on the commercial carbon paper to obtain a supporting layer;
the process of the combing hydration treatment is as follows: adding deionized water into 60 mass percent of Polytetrafluoroethylene (PTFE) aqueous emulsion for dilution to obtain 20 mass percent of PTFE aqueous emulsion, putting carbon paper into the PTFE emulsion for soaking for 20min, and then putting the carbon paper into a tubular furnace at the temperature of 350 ℃ for sintering for 30 min;
(II) preparing slurry: mixing carbon powder, absolute ethyl alcohol, a hydrophobic agent and a pore-forming agent to prepare No. 1 slurry, and mixing the carbon powder, the absolute ethyl alcohol and the hydrophobic agent to prepare No. 2 slurry;
the carbon powder is one or a mixture of several of acetylene black, carbon nano tubes, graphitized carbon and Vulcan XC-72; the hydrophobic agent is one or a mixture of more of Polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), Polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE) and polyvinylidene fluoride (1, 1-PVDF); the pore-forming agent is calcium carbonate; absolute ethyl alcohol is used as a solvent; the mass ratio of the carbon powder to the hydrophobizing agent to the pore-forming agent in the No. 1 slurry is 14:6:5 or 7: 3: 5; the mass ratio of the carbon powder to the hydrophobing agent in the No. 2 slurry is 7: 3;
(III) preparing a gas diffusion layer: spraying the slurry 1 on a support layer to form a microporous layer 1, spraying the slurry 2 on the microporous layer 1 to form a microporous layer 2, soaking in an acidic aqueous solution, drying and sintering to obtain a double-layer microporous layer type gas diffusion layer;
spraying No. 1 slurry and No. 2 slurry on the support layer and the microporous layer 1 respectively for 10 times, wherein the thickness of the microporous layer 1 and the thickness of the microporous layer 2 are both 30 micrometers; the acidic aqueous solution is one or a mixture of more of acetic acid, hydrochloric acid, oxalic acid and carbonic acid; the soaking time is 10-12 h; the drying temperature is 200 ℃ and 250 ℃, and the drying time is 20-30 min; the sintering temperature is 300-350 ℃, and the time is 20-30 min.
The pore-forming agent is added into the microporous layer 1 of the double-layer microporous layer type gas diffusion layer prepared by the invention, and the pore-forming agent is not added into the microporous layer 2, so that the pore-size gradient is facilitated, the capillary pressure of the gas diffusion layer is further improved, and the performance of the fuel cell is improved.
Compared with the prior art, the invention prepares a double-layer microporous layer structure with gradient change of pore diameter by adding pore-forming agent or not, adds the pore-forming agent into the microporous layer close to the supporting layer, improves the porosity and changes the pore diameter structure, and the microporous layer close to the catalytic layer side is prepared by adopting carbon black and PTFE, and has the following advantages: (1) compared with the conventional gas diffusion layer, the current density and the power density are higher, and the performance of the prepared fuel cell is more stable; (2) the preparation process is relatively simple, the cost is low, and the preparation method is suitable for large-scale production; (3) the repeatability is good, the preparation process of the microporous layer with the gradient aperture can be repeated, so that the repeatability of the performance of the fuel cell is higher, and the water management capability of the fuel cell is improved.
Description of the drawings:
fig. 1 is a schematic view of a principal structural principle of a membrane electrode according to the background art of the present invention.
Fig. 2 is a schematic diagram of a principle of a main structure of a gas diffusion layer according to the background art of the present invention.
Fig. 3 is a schematic diagram of the principle of the main structure of the gas diffusion layer prepared by the present invention.
Fig. 4 is an electron microscope scan of the gas diffusion layers of comparative example 1, example 1 and example 2 according to the present invention.
Fig. 5 is a graph showing performance curves of fuel cells prepared by the gas diffusion layers of comparative example 1, example 1 and example 2 according to the present invention.
Fig. 6 is a bar graph of water contact angles of fuel cells prepared by the gas diffusion layers of comparative example 1, example 1 and example 2 according to the present invention.
The specific implementation mode is as follows:
the invention is further described by way of example with reference to the accompanying drawings.
Example 1:
the specific process of the preparation method of the double-layer microporous layer gas diffusion layer according to the embodiment includes three steps of hydrophobization, slurry preparation and double-layer microporous layer preparation:
(one) hydrophobization treatment: carrying out hydrophobization treatment on commercial carbon paper to obtain a supporting layer;
(II) preparationPreparing slurry: preparing a mixed solution from 2.8g of acetylene black and 100ml of absolute ethyl alcohol, stirring for 30min, performing ultrasonic treatment for 30min again, repeating the stirring and ultrasonic treatment for 3-5 times, adding 2g of Polytetrafluoroethylene (PTFE) emulsion with the mass fraction of 60% into the mixed solution, stirring for 30min, adding 1g of CaCO3Performing ultrasonic treatment for 10min to obtain No. 1 slurry; preparing a mixed solution from 2.8g of acetylene black and 100ml of absolute ethyl alcohol, stirring for 30min, performing ultrasonic treatment for 30min again, repeating the stirring and ultrasonic treatment for 3-5 times, adding 2g of Polytetrafluoroethylene (PTFE) emulsion with the mass fraction of 60% into the mixed solution, and stirring for 30min to obtain No. 2 slurry;
(III) preparing a gas diffusion layer: spraying No. 1 slurry on a support layer to form a microporous layer 1 with the thickness of 30um, spraying No. 2 slurry on the microporous layer 1 to form a microporous layer 2 with the thickness of 30um, soaking the microporous layer 2 in a hydrochloric acid aqueous solution with the mass percentage concentration of 10% for 12 hours, placing the microporous layer in a tubular furnace, drying the microporous layer for 30 minutes at the temperature of 250 ℃, and then heating to 350 ℃ to sinter the microporous layer for 30 minutes to obtain the double-layer microporous layer type gas diffusion layer with a smooth surface.
Example 2:
the specific process of the preparation method of the double-layer microporous layer gas diffusion layer according to the embodiment includes three steps of hydrophobization, slurry preparation and double-layer microporous layer preparation:
(one) hydrophobization treatment: carrying out hydrophobization treatment on commercial carbon paper to obtain a supporting layer;
(II) preparing slurry: preparing a mixed solution from 2.8g of acetylene black and 100ml of absolute ethyl alcohol, stirring for 30min, performing ultrasonic treatment for 30min again, repeating the stirring and ultrasonic treatment for 3-5 times, adding 2g of Polytetrafluoroethylene (PTFE) emulsion with the mass fraction of 60% into the mixed solution, stirring for 30min, adding 2g of CaCO3Performing ultrasonic treatment for 20min to obtain No. 1 slurry; preparing a mixed solution from 2.8g of acetylene black and 100ml of absolute ethyl alcohol, stirring for 30min, performing ultrasonic treatment for 30min again, repeating the stirring and ultrasonic treatment for 3-5 times, adding 2g of Polytetrafluoroethylene (PTFE) emulsion with the mass fraction of 60% into the mixed solution, and stirring for 30min to obtain No. 2 slurry;
(IV) preparing a gas diffusion layer: spraying No. 1 slurry on a support layer to form a microporous layer 1 with the thickness of 30um, spraying No. 2 slurry on the microporous layer 1 to form a microporous layer 2 with the thickness of 30um, soaking the microporous layer 2 in a hydrochloric acid aqueous solution with the mass percentage concentration of 10% for 12 hours, placing the microporous layer in a tubular furnace, drying the microporous layer for 30 minutes at the temperature of 250 ℃, and then heating to 350 ℃ to sinter the microporous layer for 30 minutes to obtain the double-layer microporous layer type gas diffusion layer with a smooth surface.
Example 3:
this example relates to a pore size distribution test of a gas diffusion layer, taking a conventional gas diffusion layer as comparative example 1, scanning the gas diffusion layer of comparative example 1 and the gas diffusion layers prepared in examples 1 and 2, respectively, using a scanning electron microscope to obtain an electron microscope scan chart as shown in fig. 4 and a pore size distribution comparison table as shown in table 1:
table 1: comparative example 1, comparative example 1 and comparative example 2 pore size distribution table
| ML/g/um | 0.07-0.5 | 0.5-7 | 7-20 | Total up to |
| Comparative example 1 | 0.194 | 0.007 | 0.155 | 1.000 |
| Example 1 | 0.024 | 0.210 | 0.593 | 1.583 |
| Example 2 | 0.015 | 0.032 | 0.173 | 1.181 |
The gas diffusion layers prepared in examples 1 and 2 have a greatly increased ratio of pores between 0.5 to 7um and 7 to 20um, the number of pores is also significantly increased, the surface has a significant pore distribution, and the surface of the gas diffusion layer of comparative example 1 has only a crack distribution, indicating that: the preparation method of the double-layer microporous layer type gas diffusion layer can prepare the gas diffusion layer with the aperture changed in a gradient manner, and the aperture changed in the gradient manner can improve the gas transmission and water management capacity of the gas diffusion layer, so that the performance of the fuel cell can be improved, and the preparation method has good feasibility.
Example 4:
this example relates to the performance test of fuel cell, and the gas diffusion layer of comparative example 1 and the gas diffusion layers prepared in examples 1 and 2 were assembled with membrane electrode three-in-one CCM to form MEA for testing, wherein the membrane electrode is the CCM of the himalayan, wuhan, himalayan, opto-electronic technology, ltd, and the test conditions included: the excess coefficient of the flow rates of the cathode gas and the anode gas was 5, and the flow rate on the oxygen side was 20mL/min/cm2The flow rate on the hydrogen side was 50mL/min/cm2The back pressure is 0.0bar, the activation is carried out for 2 hours under 0.4V, and 100 percent of humidification is carried out; as the performance curve shown in fig. 5 and the water contact angle value shown in fig. 6 are obtained, it is understood that the limiting current density and the water contact angle of the gas diffusion layers prepared in example 1 and example 2 are greater, and the fuel cell performance is significantly better than that of the gas diffusion layer of comparative example 1, indicating that: the gas diffusion layers prepared in examples 1 and 2 have better gas transport and water management capabilities and good hydrophobicity, and can improve the power generation efficiency of the fuel cell。
Claims (4)
1. A preparation method of a double-layer microporous layer type gas diffusion layer is characterized in that the process comprises three steps of hydrophobization treatment, slurry preparation and double-layer microporous layer preparation:
(one) hydrophobization treatment: carrying out combing hydration treatment on the commercial carbon paper to obtain a supporting layer;
(II) preparing slurry: mixing carbon powder, absolute ethyl alcohol, a hydrophobic agent and a pore-forming agent to prepare No. 1 slurry, and mixing the carbon powder, the absolute ethyl alcohol and the hydrophobic agent to prepare No. 2 slurry;
(III) preparing a gas diffusion layer: and spraying the slurry 1 on a support layer to form a microporous layer 1, spraying the slurry 2 on the microporous layer 1 to form a microporous layer 2, soaking in an acidic aqueous solution, drying and sintering to obtain the double-layer microporous layer type gas diffusion layer.
2. The method for preparing a gas diffusion layer with a double-layer microporous layer according to claim 1, wherein the combing and hydrating process of step (a) is as follows: adding deionized water into PTFE aqueous emulsion with the mass fraction of 60% for dilution to obtain PTFE aqueous emulsion with the mass fraction of 20%, putting carbon paper into the PTFE aqueous emulsion for soaking for 20min, and then putting the carbon paper into a tubular furnace with the temperature of 350 ℃ for sintering for 30 min.
3. The method for preparing a two-layer microporous layer type gas diffusion layer according to claim 1, wherein the carbon powder in the step (two) is one or a mixture of acetylene black, carbon nanotubes, graphitized carbon and Vulcan XC-72; the hydrophobic agent is one or a mixture of more of polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer and polyvinylidene fluoride 1, 1-difluoroethylene; the pore-forming agent is calcium carbonate; absolute ethyl alcohol is used as a solvent; the mass ratio of the carbon powder to the hydrophobizing agent to the pore-forming agent in the No. 1 slurry is 14:6:5 or 7: 3: 5; the mass ratio of the carbon powder to the hydrophobing agent in the No. 2 slurry is 7: 3.
4. the method for preparing a two-layer microporous layer type gas diffusion layer according to claim 1, wherein step (three) sprays slurry No. 1 and slurry No. 2 onto the support layer and microporous layer 1, respectively, 10 times, and the thickness of each of microporous layer 1 and microporous layer 2 is 30 um; the acidic aqueous solution is one or a mixture of more of acetic acid, hydrochloric acid, oxalic acid and carbonic acid; the soaking time is 10-12 h; the drying temperature is 200 ℃ and 250 ℃, and the drying time is 20-30 min; the sintering temperature is 300-350 ℃, and the time is 20-30 min.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111408725A (en) * | 2020-04-27 | 2020-07-14 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method of gas diffusion layer for SPE electrolytic cell with gradient aperture |
| CN112117465A (en) * | 2020-08-06 | 2020-12-22 | 江苏大学 | A kind of fuel cell gas diffusion layer and processing method |
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| CN112117465A (en) * | 2020-08-06 | 2020-12-22 | 江苏大学 | A kind of fuel cell gas diffusion layer and processing method |
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| CN113991127A (en) * | 2021-10-28 | 2022-01-28 | 无锡威孚高科技集团股份有限公司 | Gas diffusion layer of proton exchange membrane fuel cell and preparation method thereof |
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| CN114243044A (en) * | 2021-12-21 | 2022-03-25 | 中国科学院山西煤炭化学研究所 | A gas diffusion layer for improving the water management capability of a fuel cell and a preparation method thereof |
| CN114243044B (en) * | 2021-12-21 | 2023-12-26 | 中国科学院山西煤炭化学研究所 | Gas diffusion layer for improving water management capacity of fuel cell and preparation method thereof |
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| CN114725399B (en) * | 2022-04-28 | 2023-10-17 | 一汽解放汽车有限公司 | Low-temperature cold start adaptive gas diffusion layer, preparation method thereof and fuel cell |
| CN114725398A (en) * | 2022-04-28 | 2022-07-08 | 一汽解放汽车有限公司 | High-pressure-resistant long-life gas diffusion layer, preparation method and fuel cell |
| CN114976060A (en) * | 2022-07-04 | 2022-08-30 | 一汽解放汽车有限公司 | Preparation method and application of gas diffusion layer |
| CN114976060B (en) * | 2022-07-04 | 2024-05-28 | 一汽解放汽车有限公司 | Preparation method and application of gas diffusion layer |
| CN115425239A (en) * | 2022-09-01 | 2022-12-02 | 海卓动力(北京)能源科技有限公司 | Preparation method of microporous layer with hydrophobic and air permeability double gradients |
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