CN111162285A - Conductive gas diffusion layer of fuel cell and preparation method thereof - Google Patents

Conductive gas diffusion layer of fuel cell and preparation method thereof Download PDF

Info

Publication number
CN111162285A
CN111162285A CN201811327143.8A CN201811327143A CN111162285A CN 111162285 A CN111162285 A CN 111162285A CN 201811327143 A CN201811327143 A CN 201811327143A CN 111162285 A CN111162285 A CN 111162285A
Authority
CN
China
Prior art keywords
diffusion layer
gas diffusion
conductive
porous
electrically conductive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811327143.8A
Other languages
Chinese (zh)
Other versions
CN111162285B (en
Inventor
王素力
李焕巧
孙公权
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201811327143.8A priority Critical patent/CN111162285B/en
Publication of CN111162285A publication Critical patent/CN111162285A/en
Application granted granted Critical
Publication of CN111162285B publication Critical patent/CN111162285B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023Porous and characterised by the material
    • H01M8/0241Composites
    • H01M8/0245Composites in the form of layered or coated products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8803Supports for the deposition of the catalytic active composition
    • H01M4/8807Gas diffusion layers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

The invention provides a fuel cell conductive gas diffusion layer and a preparation method thereof, wherein the diffusion layer comprises a porous conductive substrate and a conductive porous microporous layer attached to at least one side of the porous conductive substrate, and the porous conductive substrate is a carbon fiber fabric, a carbon paper or a carbon cloth; the carbon fiber fabric is woven or non-woven. The method realizes the uniform distribution of the electronic conductive material and the hydrophobic high molecular binder in the microporous layer on the micro-nano scale, avoids the local agglomeration and phase separation of the two, has accurate and controllable composition and structure on the micro-nano scale of the microporous layer of the prepared gas diffusion layer, can be designed at will to meet the functional requirements of gas-liquid transmission of the gas diffusion layer, and avoids the flooding of the fuel cell in the discharging process.

Description

Conductive gas diffusion layer of fuel cell and preparation method thereof
Technical Field
The invention relates to the field of electrochemistry, in particular to a gas diffusion layer, a preparation method thereof and a fuel cell.
Background
The fuel cell is an electrochemical reaction device which directly converts chemical energy of fuel molecules into electric energy, and has the advantages of high energy efficiency, small environmental pollution and the like. Compared with other types of fuel cells, the anode reaction of the proton exchange membrane fuel is the oxidation reaction of hydrogen, the cathode reaction of oxygen, and the discharged product is water, so that the proton exchange membrane fuel is a clean energy and is expected to be widely applied to vehicle-mounted power, military equipment, mobile and portable energy equipment.
The membrane electrode is the core component of the proton exchange membrane fuel cell and mainly comprises a solid proton exchange membrane, a catalyst layer and a gas diffusion layer. The porous gas diffusion layer mainly plays a role in supporting a catalyst layer and stabilizing an electrode structure in the membrane electrode, and simultaneously provides a plurality of functions such as reactant introducing and distributing channels, electronic channels and product discharging channels for electrode reaction, and is one of core components of the membrane electrode. The common gas diffusion layer comprises a conductive substrate and a microporous layer, wherein the common substrate materials comprise carbon fiber paper, carbon fiber cloth, carbon fiber felt and the like, and the common substrate materials mainly have the function of supporting, so that the gas diffusion electrode has certain mechanical strength and shape; the microporous layer is typically formed by applying a mixture of a hydrophobic polymeric binder and conductive carbon particles to a conductive substrate by screen printing, spraying or coating processes. In the discharging process of the fuel cell, the gas diffusion layer needs to discharge the generated product water out of the cell in time while introducing and distributing the reaction gas (hydrogen and air) so as to prevent the generated water vapor from condensing into water drops to block the pore channels of the gas diffusion layer, further influence the supply of the reaction gas to the catalyst layer and the catalyst surface, cause flooding of the electrode, and influence the discharging performance and the service life of the cell.
The microporous membrane layer can partially fill and level the macroporous structure of the support layer, thus reducing the roughness and pore structure of the support layer, according to the Young-Laplace equation (△ p ═ γ/r), the larger the radius of the hydrophobic pore r, the pressure difference between the inner surface and the outer surface of the liquid, the smaller the pores, the more easily the pores are coalesced by the liquid, the more easily the pores are coalesced, the liquid permeation and the liquid permeation of the porous structure of the support layer are leveled, the liquid permeation and the pore structure of the porous membrane electrode are leveled, the more the pores are wetted by the liquid, the liquid permeation and the pore structure of the porous membrane electrode are leveled, the more the gas permeation and the pore structure of the porous membrane electrode are leveled, the more the roughness of the porous membrane electrode is increased, the roughness of the porous membrane electrode surface of the conductive microporous membrane electrode is increased, the surface of the conductive carbon powder is increased, the porous carbon powder is easily soaked in the porous carbon powder, the porous membrane electrode is soaked in the porous membrane electrode, the porous membrane electrode is not only the porous membrane electrode is filled, the porous membrane electrode is not saturated, the porous carbon powder is dissolved in the porous carbon powder, the porous carbon powder is dispersed in the porous membrane electrode, the porous membrane is dispersed carbon powder, the porous membrane is dispersed carbon powder, the porous membrane is dispersed carbon powder is dispersed, the porous membrane is dispersed, the surface of the porous.
In order to improve the uniformity of the pore structure of the microporous layer and the surface roughness thereof, patent document 1 (jp 2015-79639 a) proposes a preparation technology of a gas diffusion electrode, which comprises forming a microporous layer on the surface of a support layer by a doctor blade coating method, and then reducing the surface roughness by punch forming, but the pore structure of the microporous layer is easily damaged in the punch forming process, so that the diffusion performance of reaction gas is reduced, and the discharge performance of a battery is further influenced; chinese patent No. CN107851805 discloses a method for improving the surface roughness of a gas diffusion layer by constructing a dual microporous layer strategy, wherein the first microporous layer in contact with a conductive substrate layer mainly comprises conductive carbon spheres, and the second microporous layer comprises a conductive material with a linear structure (the aspect ratio of the linear conductive material is 30-5000). According to the scheme, either the forming process of the gas diffusion layer is adopted, or the structure composition of the gas diffusion layer is adjusted, the microporous layer is changed from a single layer to multiple layers, the roughness of the surface of the microporous layer is reduced, the regulation and control of the macroscopic pore structure and the roughness of the microporous layer are strengthened in the aspect of adjusting the micro-area components/structures of the main components of the microporous layer, the designability of the gas diffusion layer is low, and the calculation and the optimization design are difficult to be carried out by combining the theoretical simulation technology of material transfer.
Disclosure of Invention
The invention provides a conductive gas diffusion layer of a fuel cell and a preparation method thereof, which can overcome the problems and defects in the prior art. The gas diffusion layer takes porous carbon paper or carbon cloth as a substrate material, and the uniform distribution of a conductive carbon material and a hydrophobic binder in a microporous layer is improved by regulating and controlling the slurry composition and the preparation method of the microporous layer, so that the uniform distribution of the conductive carbon material and the hydrophobic high molecular binder in the microporous layer on a micro-nano scale is realized, and the local agglomeration and phase separation of the conductive carbon material and the hydrophobic high molecular binder are avoided; the prepared microporous layer of the gas diffusion layer can realize accurate and controllable composition and structure on micro-scale and nano-scale, and can be designed at will to meet the functional requirements of gas-liquid transmission for the gas diffusion layer; the uniform distribution of the high molecular binder in the microporous layer is beneficial to the formation of a gas diffusion layer hydrophobic network, so as to avoid flooding in the discharge process of the fuel cell; in addition, the gas diffusion layer obtained based on the microporous layer slurry and the preparation method has small surface roughness, and the electrolyte membrane damage phenomenon in the hot pressing forming process of the membrane electrode is avoided.
In one aspect, the present invention provides a fuel cell conductive gas diffusion layer comprising a porous conductive substrate, and further comprising an electrically conductive porous microporous layer attached to at least one side of the porous conductive substrate; the porous conductive substrate is a carbon fiber fabric, carbon paper or carbon cloth; the carbon fiber fabric is woven or non-woven.
Based on the technical scheme, preferably, the conductive porous microporous layer consists of a conductive carbon material and a high molecular binder; the mass ratio of the conductive carbon material to the polymer binder is 6:4-9: 1. The conductive carbon powder and the macromolecular binder in the microporous layer of the gas diffusion layer are uniformly distributed on a micro-nano scale, and the components do not have local agglomeration and phase separation behaviors.
Based on the technical scheme, it is further preferable that the conductive carbon material is one or a mixture of more than two of conductive activated carbon, graphite, multi-walled carbon nanotubes, single-walled carbon nanotubes, graphene, reduced graphite oxide and conductive carbon aerosol; the polymer binder is one or a mixture of more than two of polytetrafluoroethylene, polyvinylidene fluoride and derivatives with similar structures.
Based on the technical scheme, it is further preferable that the conductive carbon material and the polymer binder are uniformly distributed on the nano scale of the porous microporous layer, and the particle size of the polymer binder is 50-300 nm.
Based on the technical scheme, it is further preferable that the conductive carbon material and the polymer binder are uniformly distributed on the nano scale of the porous microporous layer, and the particle size of the polymer binder is 50-100 nm.
Based on the technical scheme, the diameter of the carbon fiber fabric is preferably 5-15um, and the length of the carbon fiber fabric is preferably 100-1000 um.
The invention also provides a preparation method of the conductive gas diffusion layer of the fuel cell, which comprises the following steps:
(1) soaking the porous conductive substrate in a macromolecular binder aqueous solution, adsorbing for 5-10min at room temperature, taking out and drying to obtain the porous conductive substrate soaked with the macromolecular binder;
(2) dispersing a conductive carbon material, a high-molecular binder solution and a water-soluble surfactant in an aqueous solution, fully mixing and stirring, heating to 50-90 ℃, continuously mechanically stirring for 1-2 hours, cooling to room temperature, performing solid-liquid separation to obtain a filter cake of microporous layer slurry, dispersing the filter cake in an alcohol-water mixed solution, performing uniform ultrasonic dispersion, and coating the filter cake on the porous conductive substrate impregnated with the high-molecular binder in the step (1) to obtain a gas diffusion layer precursor;
(3) and drying the gas diffusion layer precursor in an oven, then rolling and leveling the gas diffusion layer, and continuing to perform heat treatment to reduce the roughness of the surface of the microporous layer and remove a surfactant, and simultaneously fusing the conductive substrate and the high-molecular binder in the microporous layer into a three-dimensional network to obtain the integrated gas diffusion layer.
Based on the above technical scheme, preferably, the heat treatment temperature in the step (3) is 200-400 ℃, and the treatment time is 10-60 min; the heat treatment is carried out by one or more than two mixed gases of air, oxygen, argon and nitrogen.
Based on the technical scheme, preferably, the concentration of the water-soluble surfactant in the reaction system 1 is 0.01-1000 mmol/L; the reaction concentration of the conductive carbon material in the reaction system 1 is 0.1g/L-2 g/L; the concentration of the macromolecular binder in a reaction system is 0.01g/L-0.2 g/L.
Based on the technical scheme, preferably, the water-soluble surfactant is one or a mixture of more than two of cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, potassium stearate, sodium oleoyl polyamino acid, sodium dodecyl aminopropionate, sodium lauryl sulfate, polyethylene oxide lauroyl ether, sorbitan laurate, diethanolamide oleate, dodecyl dimethyl betaine, tetradecyl dimethyl sulfoethyl betaine, derivatives and analogs thereof. Based on the above technical scheme, it is further preferable that the temperature of the heat treatment is 300-340 ℃; the time of the heat treatment is 20-50 minutes.
Advantageous effects
(1) The method realizes the uniform dispersion and mixing of the conductive carbon material and the hydrophobic high molecular binder by virtue of the action of the water-soluble surfactant in the preparation process of the microporous layer slurry, and the electronic conductive material and the hydrophobic high molecular binder in the conductive porous microporous layer prepared based on the slurry are uniformly distributed on a micro-nano scale, so that the local agglomeration and phase separation of the conductive carbon material and the hydrophobic high molecular binder are effectively avoided; the uniform distribution of the high molecular binder in the microporous layer is beneficial to the formation of a gas diffusion layer hydrophobic network, the composition and the structure of the microporous layer of the gas diffusion layer prepared based on the microporous layer are accurate and controllable in micro-scale and nano-scale, and the microporous layer can be designed at will to meet the functional requirements of gas-liquid transmission of the gas diffusion layer and avoid flooding in the discharging process of the fuel cell.
(2) The gas diffusion layer obtained based on the method has small surface roughness, and can avoid the damage phenomenon of an electrolyte membrane in the membrane electrode forming process.
Drawings
Fig. 1 is a microscopic structure view of a microporous layer of a gas diffusion layer prepared in comparative example 1.
Fig. 2 is a microscopic structure view of the gas diffusion layer prepared in example 1.
Detailed Description
Comparative example 1
Cutting 5cm by 5cm of conductive carbon paper Toray060, then soaking the conductive carbon paper Toray060 in 5 wt% of PTFE aqueous solution (100ml), taking out the conductive carbon paper after 5min, drying the conductive carbon paper for later use by a blower, placing the conductive carbon paper in a high-temperature furnace, and carrying out heat treatment at 340 ℃ in an air atmosphere to ensure that the Toray060 carbon paper has hydrophobicity; 50mg of XC-72R conductive carbon black and 200mg of PTFE aqueous solution (the concentration is 5 wt%) are dispersed in 5ml of ethanol, and after uniform ultrasonic dispersion, the mixture is kept stand for 30min, then the supernatant is removed to obtain microporous layer slurry, the slurry is uniformly coated on one side of hydrophobic Toray060 carbon paper by a blade coating method, and then heat treatment is carried out, wherein the treatment temperature is 350 ℃, the atmosphere is air, and the treatment time is 30 min. By SEM characterization of the gas diffusion layer, the microstructure is shown in FIG. 1, and the microporous layer is found to have uneven surface on the carbon paper support layer and a large amount of microporous structure, with a maximum pore size of about 3-5 μm.
Example 1
Cutting 5cm by 5cm of conductive carbon paper Toray060, then soaking the conductive carbon paper Toray060 in 5 wt% of PTFE aqueous solution (100ml), taking out after 5min, and drying the conductive carbon paper by using a blower for standby; dispersing 50mg of XC-72R conductive carbon black and 200mg of PTFE aqueous solution (the concentration is 5 wt%) in 50ml of aqueous solution, after uniform ultrasonic dispersion, adding 10mg of sodium dodecyl sulfate, continuing to stir for 30min, heating the mixed solution to 80 ℃, continuing to mechanically stir for 2 h, reducing the temperature, filtering the obtained solution to obtain a wet filter cake with the water content of 40%, putting the wet filter cake into 4ml of ethanol-water mixed solution for ultrasonic dispersion to obtain microporous layer slurry, uniformly coating the slurry on one side of hydrophobic Toray060 carbon paper by using a blade coating method, drying the water in an oven, rolling and leveling the slurry, and then putting the Toray060 carbon paper into a certain atmosphere for heat treatment at the treatment temperature of 350 ℃ in the atmosphere of air for 30 min. The gas diffusion layer is characterized by SEM, the microstructure of the gas diffusion layer is shown in figure 2, and the microporous layer can be found to be uniformly distributed on the surface of the carbon paper support layer, the pore structure is relatively uniform and ordered, and the maximum pore diameter is less than 1 micron.
Example 2
Cutting conductive carbon paper SGL 29AA with the thickness of 5cm by 5cm, then soaking the conductive carbon paper SGL 29AA in 5 wt% of PTFE aqueous solution (80ml), taking out after 7min, and drying the conductive carbon paper SGL by using a blower for later use; dispersing 50mg of acetylene black conductive carbon black and 100mg of PTFE aqueous solution (the concentration is 10 wt%) in 50ml of aqueous solution, adding 12mg of polyethylene oxide lauroyl ether after uniform ultrasonic dispersion, continuing to stir for 30min, heating the mixed solution to 60 ℃, continuing to mechanically stir for 1 hour, cooling, filtering the obtained solution to obtain a wet filter cake with the water content of 40%, placing the filter cake in 5ml of ethanol-water mixed solution for ultrasonic dispersion to obtain microporous layer slurry, uniformly coating the slurry on one side of hydrophobic SGL 29AA carbon paper by using a blade coating method, drying the water in an oven, rolling and flattening the water, then placing the mixture in a certain atmosphere for heat treatment, wherein the treatment temperature is 300 ℃, and the atmosphere is the mixture of air and argon (the volume ratio is 1:1) for 30 min. The obtained microporous layer in the gas diffusion layer is uniformly distributed on the surface of the carbon paper support layer, the pore structure is relatively uniform and ordered, and the maximum pore diameter is not more than 1 micron.
Example 3
Cutting out 5 cm-5 cm conductive carbon fiber cloth, then soaking the conductive carbon fiber cloth in 7 wt% PTFE aqueous solution (100ml), taking out after 10min, and drying by using a blower for later use; dispersing 50mg of acetylene black conductive carbon black and 100mg of PTFE aqueous solution (the concentration is 10 wt%) in 50ml of aqueous solution, adding 8mg of polyethylene oxide lauroyl ether after uniform ultrasonic dispersion, continuing to stir for 30min, heating the mixed solution to 60 ℃, continuing to mechanically stir for 1 h, cooling, filtering the obtained solution to obtain a wet filter cake with the water content of 30%, placing the filter cake in 5ml of ethanol-water mixed solution for ultrasonic dispersion to obtain microporous layer slurry, uniformly coating the slurry on one side of hydrophobic conductive carbon fiber cloth by using a blade coating method, drying the water in an oven, rolling and leveling the hydrophobic conductive carbon fiber cloth, and then placing the hydrophobic conductive carbon fiber cloth in a certain atmosphere for heat treatment at the treatment temperature of 300 ℃ in the atmosphere of oxygen for 50 min. The obtained microporous layer in the gas diffusion layer is uniformly distributed on the surface of the carbon paper support layer, the pore structure is relatively uniform and ordered, and the maximum pore diameter is not more than 1 micron. .
Example 4
Cutting conductive carbon paper SGL 29AA with the thickness of 5cm by 5cm, then soaking the conductive carbon paper SGL 29AA in 5 wt% of PTFE aqueous solution (80ml), taking out after 7min, and drying the conductive carbon paper SGL by using a blower for later use; dispersing 50mg of acetylene black conductive carbon black and 100mg of PTFE aqueous solution (the concentration is 10 wt%) in 50ml of aqueous solution, adding 12mg of polyethylene oxide lauroyl ether after uniform ultrasonic dispersion, continuing to stir for 30min, heating the mixed solution to 70 ℃, continuing to mechanically stir for 1 hour, cooling, filtering the obtained solution to obtain a wet filter cake with the water content of 20%, placing the filter cake in 5ml of ethanol-water mixed solution for ultrasonic dispersion to obtain microporous layer slurry, uniformly coating the slurry on one side of hydrophobic SGL 29AA carbon paper by using a blade coating method, drying the water in an oven, rolling and flattening the water, then placing the mixture in a certain atmosphere for heat treatment, wherein the treatment temperature is 270 ℃, and the atmosphere is the mixture of air and argon (the volume ratio is 1:1) for 30 min. The obtained microporous layer in the gas diffusion layer is uniformly distributed on the surface of the carbon paper support layer, the pore structure is relatively uniform and ordered, and the maximum pore diameter is not more than 800 nanometers.
Example 5
Cutting conductive carbon paper SGL 29AA with the thickness of 5cm by 5cm, then soaking the conductive carbon paper SGL 29AA in 5 wt% of PTFE aqueous solution (80ml), taking out after 7min, and drying the conductive carbon paper SGL by using a blower for later use; dispersing 50mg of acetylene black conductive carbon black and 100mg of PTFE aqueous solution (the concentration is 10 wt%) in 50ml of aqueous solution, adding 12mg of polyethylene oxide lauroyl ether after uniform ultrasonic dispersion, continuing to stir for 30min, heating the mixed solution to 60 ℃, continuing to mechanically stir for 1 hour, cooling, filtering the obtained solution to obtain a wet filter cake with the water content of 60%, placing the filter cake in 5ml of ethanol-water mixed solution for ultrasonic dispersion to obtain microporous layer slurry, uniformly coating the slurry on one side of hydrophobic SGL 29AA carbon paper by using a blade coating method, drying the water in an oven, rolling and flattening the water, and then placing the mixture in a certain atmosphere for heat treatment, wherein the treatment temperature is 350 ℃, the atmosphere is argon (the volume ratio is 1:1), and the time is 20 min. The obtained microporous layer in the gas diffusion layer is uniformly distributed on the surface of the carbon paper support layer, the pore structure is relatively uniform and ordered, and the maximum pore diameter is not more than 900 nanometers.

Claims (10)

1. A fuel cell electrically conductive diffusion layer comprising a porous electrically conductive substrate, and further comprising an electrically conductive porous microporous layer attached to at least one side of the porous electrically conductive substrate.
2. The electrically conductive gas diffusion layer according to claim 1, wherein the electrically conductive porous microporous layer is composed of an electrically conductive carbon material and a polymeric binder; the mass ratio of the conductive carbon material to the polymer binder is 6:4-9: 1.
3. The conductive gas diffusion layer according to claim 2, wherein the conductive carbon material is one or a mixture of two or more of conductive activated carbon, graphite, multi-walled carbon nanotubes, single-walled carbon nanotubes, graphene, reduced graphite oxide, and conductive carbon aerosol; the high molecular binder is one or a mixture of more than two of polytetrafluoroethylene and polyvinylidene fluoride.
4. The electrically conductive gas diffusion layer according to claim 2, wherein the particle size of the polymeric binder is 50-300 nm.
5. The electrically conductive gas diffusion layer according to claim 4, wherein the particle size of said polymeric binder is 50-100 nm.
6. A method of preparing a fuel cell conductive gas diffusion layer according to any one of claims 1 to 5, comprising the steps of:
(1) soaking the porous conductive substrate in a high-molecular binder aqueous solution, treating at room temperature for 5-10min, taking out, and drying to obtain the porous conductive substrate soaked with the high-molecular binder;
(2) dispersing a conductive carbon material, a high-molecular binder solution and a water-soluble surfactant in an aqueous solution to obtain a reaction system 1, fully mixing and stirring, heating to 50-90 ℃, continuing to mechanically stir for 1-2 hours, cooling to room temperature, performing solid-liquid separation to obtain a filter cake of microporous layer slurry, dispersing the filter cake in an ethanol/water mixed solution, performing ultrasonic dispersion uniformly, and coating the mixture on the porous conductive substrate impregnated with the high-molecular binder obtained in the step (1) to obtain a gas diffusion layer precursor;
(3) and drying the gas diffusion layer precursor, rolling and flattening, and performing heat treatment to obtain the conductive gas diffusion layer of the fuel cell.
7. The method as claimed in claim 6, wherein the heat treatment temperature in the step (3) is 200-400 ℃, and the treatment time is 10-60 min; the gas for heat treatment is one or a mixture of more than two of air, oxygen, argon and nitrogen.
8. The preparation method according to claim 6, wherein the concentration of the water-soluble surfactant in the step (2) in the reaction system 1 is 0.01 to 1000 mmol/L; the reaction concentration of the conductive carbon material in the reaction system 1 is 0.1g/L-2 g/L.
9. The method according to claim 6, wherein the water-soluble surfactant is one or a mixture of two or more of cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride, sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, potassium stearate, sodium oleoyl polyamino acid, sodium dodecylaminopropionate, sodium lauryl sulfate, polyoxyethylene lauryl ether, sorbitan laurate, diethanolamide oleate, dodecyldimethylbetaine, tetradecyldimethylsulfoethylbetaine, and derivatives thereof.
10. The method as claimed in claim 7, wherein the temperature of the heat treatment is 300-340 ℃; the time of the heat treatment is 20-50 minutes.
CN201811327143.8A 2018-11-08 2018-11-08 Conductive gas diffusion layer of fuel cell and preparation method thereof Active CN111162285B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811327143.8A CN111162285B (en) 2018-11-08 2018-11-08 Conductive gas diffusion layer of fuel cell and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811327143.8A CN111162285B (en) 2018-11-08 2018-11-08 Conductive gas diffusion layer of fuel cell and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111162285A true CN111162285A (en) 2020-05-15
CN111162285B CN111162285B (en) 2021-06-04

Family

ID=70555145

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811327143.8A Active CN111162285B (en) 2018-11-08 2018-11-08 Conductive gas diffusion layer of fuel cell and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111162285B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112928285A (en) * 2021-03-10 2021-06-08 上海电气集团股份有限公司 Gas diffusion layer, preparation method thereof, fuel cell anode and fuel cell
CN113809336A (en) * 2021-08-23 2021-12-17 安徽大学 Carbon fiber and graphene compounded high-strength porous material and gas diffusion layer and preparation method thereof
CN114927704A (en) * 2022-05-12 2022-08-19 上海碳际实业集团有限公司 Preparation method of gas diffusion layer for fuel cell
CN114953635A (en) * 2022-05-30 2022-08-30 安徽天富环保科技材料有限公司 Activated carbon fiber cloth for gas diffusion of new energy battery
CN115000446A (en) * 2022-07-22 2022-09-02 上海电气集团股份有限公司 Gas diffusion layer, preparation method thereof, membrane electrode, cell and application
CN114927704B (en) * 2022-05-12 2024-11-15 上海碳际实业集团有限公司 Preparation method of gas diffusion layer for fuel cell

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1949570A (en) * 2005-10-10 2007-04-18 中国科学院大连化学物理研究所 Gas diffusion layer for low temp fuel cell and preparing process thereof
CN1988225A (en) * 2005-12-23 2007-06-27 中国科学院大连化学物理研究所 Gas diffusion layer for proton exchanging film fuel cell and its preparing method
CN101325259A (en) * 2007-06-13 2008-12-17 中国科学院大连化学物理研究所 Method for preparing gaseous diffusion layer of fuel battery with proton exchange film
CN101411016A (en) * 2006-02-02 2009-04-15 协进I&C株式会社 Preparation of gas diffusion layer for fuel cell
CN106134492B (en) * 2006-09-13 2011-11-23 上海空间电源研究所 A kind of preparation method of hydrophilic film electrode
WO2018186293A1 (en) * 2017-04-03 2018-10-11 東レ株式会社 Method for producing gas diffusion electrode substrate, and fuel cell

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1949570A (en) * 2005-10-10 2007-04-18 中国科学院大连化学物理研究所 Gas diffusion layer for low temp fuel cell and preparing process thereof
CN1988225A (en) * 2005-12-23 2007-06-27 中国科学院大连化学物理研究所 Gas diffusion layer for proton exchanging film fuel cell and its preparing method
CN101411016A (en) * 2006-02-02 2009-04-15 协进I&C株式会社 Preparation of gas diffusion layer for fuel cell
CN106134492B (en) * 2006-09-13 2011-11-23 上海空间电源研究所 A kind of preparation method of hydrophilic film electrode
CN101325259A (en) * 2007-06-13 2008-12-17 中国科学院大连化学物理研究所 Method for preparing gaseous diffusion layer of fuel battery with proton exchange film
WO2018186293A1 (en) * 2017-04-03 2018-10-11 東レ株式会社 Method for producing gas diffusion electrode substrate, and fuel cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
徐海峰: ""质子交换膜燃料电池微孔层制备方法的研究"", 《中国优秀硕士学位论文全文数据库(电子期刊) 工程科技2辑》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112928285A (en) * 2021-03-10 2021-06-08 上海电气集团股份有限公司 Gas diffusion layer, preparation method thereof, fuel cell anode and fuel cell
CN113809336A (en) * 2021-08-23 2021-12-17 安徽大学 Carbon fiber and graphene compounded high-strength porous material and gas diffusion layer and preparation method thereof
CN113809336B (en) * 2021-08-23 2023-10-24 安徽大学 High-strength porous material compounded by carbon fibers and graphene and gas diffusion layer and preparation method thereof
CN114927704A (en) * 2022-05-12 2022-08-19 上海碳际实业集团有限公司 Preparation method of gas diffusion layer for fuel cell
CN114927704B (en) * 2022-05-12 2024-11-15 上海碳际实业集团有限公司 Preparation method of gas diffusion layer for fuel cell
CN114953635A (en) * 2022-05-30 2022-08-30 安徽天富环保科技材料有限公司 Activated carbon fiber cloth for gas diffusion of new energy battery
CN114953635B (en) * 2022-05-30 2023-09-15 安徽天富环保科技材料有限公司 Activated carbon fiber cloth for gas diffusion of new energy battery
CN115000446A (en) * 2022-07-22 2022-09-02 上海电气集团股份有限公司 Gas diffusion layer, preparation method thereof, membrane electrode, cell and application
CN115000446B (en) * 2022-07-22 2024-05-31 上海电气集团股份有限公司 Gas diffusion layer, preparation method thereof, membrane electrode, battery and application

Also Published As

Publication number Publication date
CN111162285B (en) 2021-06-04

Similar Documents

Publication Publication Date Title
CN110148759B (en) Preparation method of high-current-density-oriented proton exchange membrane fuel cell gas diffusion layer
CN111162285B (en) Conductive gas diffusion layer of fuel cell and preparation method thereof
Uchida et al. Improved preparation process of very‐low‐platinum‐loading electrodes for polymer electrolyte fuel cells
CN1970443B (en) Mesoporous carbon, manufacturing method thereof, and fuel cell using the same
CN102104159A (en) Novel gas diffusion layer used for fuel cell, preparation and application
CA2979528C (en) Support carbon material and catalyst for solid polymer type fuel cell use
JP2011525468A (en) Controllable synthesis of porous carbon spheres and their electrochemical application
CN113241448A (en) Gradient microporous gas diffusion layer of proton exchange membrane fuel cell and preparation method thereof
CN108780900B (en) Carbon powder for fuel cell, and catalyst, electrode catalyst layer, membrane electrode assembly, and fuel cell using same
Wang et al. Hierarchically porous carbon microspheres with fully open and interconnected super-macropores for air cathodes of Zn-Air batteries
CN109786762B (en) Structure of gradient hydrophilic-hydrophobic/air electrode and preparation method thereof
CN115513477B (en) Microporous layer slurry of proton exchange membrane fuel cell, gas diffusion layer and preparation method of microporous layer slurry
Jung et al. Optimization of nafion ionomer content using synthesized Pt/carbon nanofibers catalyst in polymer electrolyte membrane fuel cell
KR100969029B1 (en) Membrane Electrode Assembly for Proton Exchange Membrane Fuel Cell and manufacturing method of it
Sepp et al. Enhanced stability of symmetrical polymer electrolyte membrane fuel cell single cells based on novel hierarchical microporous-mesoporous carbon supports
US8986906B2 (en) Method for preparing nanoporous Pt/TiO2 composite particles
JP2020166941A (en) Carbon material for catalyst carrier, catalyst layer for fuel cell, and fuel cell
CN116581321A (en) Fuel cell gas diffusion layer with gradient hole distribution and preparation method thereof
CN114930584B (en) Gas diffusion layer of proton exchange membrane fuel cell and preparation method thereof
CN109768288B (en) Biomorphic Ni-Li/C catalyst and preparation method and application thereof
Sepp et al. Activity and stability of carbide derived carbon supports in PEMFC application
CN104659376B (en) A kind of membrane electrode with gas flow configuration and preparation method thereof
Nam et al. Operating characteristics of direct methanol fuel cell using a platinum–ruthenium catalyst supported on porous carbon prepared from mesophase pitch
CN114256469B (en) Gas diffusion layer for fuel cell, preparation method thereof and fuel cell
CN114628690B (en) Fuel cell gas diffusion layer and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant