CN1780038A - Control of micro-craze on carbon coating when preparing GDL electrode layer of fuel cell unit - Google Patents

Control of micro-craze on carbon coating when preparing GDL electrode layer of fuel cell unit Download PDF

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Publication number
CN1780038A
CN1780038A CNA2004100960568A CN200410096056A CN1780038A CN 1780038 A CN1780038 A CN 1780038A CN A2004100960568 A CNA2004100960568 A CN A2004100960568A CN 200410096056 A CN200410096056 A CN 200410096056A CN 1780038 A CN1780038 A CN 1780038A
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Prior art keywords
carbon
particle
coating
carbon black
fuel cell
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CNA2004100960568A
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Inventor
让·弗朗索瓦·莱考斯托维克
莫里斯R·帕奎因
保罗·肯尼迪
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Albany International Techniweave Inc
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Albany International Techniweave Inc
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Priority to CNA2004100960568A priority Critical patent/CN1780038A/en
Publication of CN1780038A publication Critical patent/CN1780038A/en
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    • 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

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Abstract

A process for controlling the microcracks on coated carbon layer when the gas diffusion layer GDL of electrode for fuel battery unit is prepared features that as said GDL contains carbon block, fluoric polymer and graphite and/or carbon particles, the size of said graphite and/or carbon particle must be greater than that of carbon black obviously.

Description

During preparation cell of fuel cell GDL electrode layer to the control of carbon coating micro-crack
Technical field
The present invention relates to put on the coating on the surface of the gas diffusion layers of cell of fuel cell or battery or electrode, it contains carbon or graphite granule.
Background technology
The gas diffusion layers of cell of fuel cell or battery (" GDLs "), it can be the carbon fiber of nonwoven fabrics or form of fabric, is coated with a kind of material in a side or many sides usually, electrically contacts to form between the GDL in cell of fuel cell and barrier film or the bipolar plates.This type coating can be by carbon black (being also referred to as acetylene carbon black or amorphous carbon black) and fluoropolymer such as Telfon Mixture make.Can also comprise other materials, as particles of different sizes, to control desirable performance, as conductivity or the support catalyst that strengthens.
In order to obtain the higher fuel efficiency of cell of fuel cell or battery, should control the size and the hole of coating.Hole can influence some functions, comprising: form further path and flow to catalyst and barrier film with control fuel; Be adjusted near the water yield of barrier film; And support catalyst itself.
These coatings are to utilize the aqueous dispersion with low solid loading to make.When removing a large amount of fluids, crackle (" mud crack ") often betides the lip-deep coating of GDL.Typical crackle comprises the holiday of being made up of breaking in the cured film, and it exposes naked substrate.During the preparation coated substrate, too crisp or with the adherence of substrate when too low, above-mentioned situation can take place usually when coating.When heavier coating was deposited on the GDL substrate surface, it is more obvious that these crackles can become.Crackle is serious more, and it is just poor more that GDL finishes the effect of its some function.This class crackle example is shown in Fig. 1 in the coating on GDL surface.
Eliminate the conventional method of the crackle in the coating, used as increase adhesive, control rate of drying, continuity shallow layer (successive thin pass coatings) and increase solid, but do not see successfully.In this application, increase adhesive and can not effectively control crackle.For being effective essential rate of drying is to be difficult for implementing.The continuity shallow layer also is like this; It is also not all right to increase solid, because it hinders coating process.
Summary of the invention
According to the present invention, the gas diffusion layers that is used for cell of fuel cell or battery or the coating of electrode are provided, its crackle is reduced to minimum level.This coating comprises the aqueous dispersion of one of carbon black, fluoropolymer and graphite granule and carbon granule.The size of these particles of great majority is significantly greater than carbon black fine particle, and it can be in the scope of for example about 13~95nm.Carbon granule can be chopped carbon fiber, carbon or graphite flake or thin layer, carbon nano-tube, carbon fibrils (carbon fibrils) or carbon whisker.
These carbon granules can have higher draw ratio (length to diameter ratio).
, will become apparent according to other characteristics of the present invention and advantage the detailed description of specific embodiment from reference to the accompanying drawings, wherein identical parts are to carry out mark with identical drawing reference numeral.
Description of drawings
Fig. 1 is on the gas diffusion layers fabric, the appearance of coat of crackle is arranged;
Fig. 2 is according to a specific embodiment of the present invention, the appearance of coat on the gas diffusion layers fabric; And
Fig. 3 is the schematic diagram of an embodiment of cell of fuel cell, can apply coating of the present invention to it.
Preferred embodiment
In the present invention, aqueous dispersion is put on the substrate of the GDL of battery or cell of fuel cell (as the methanol fuel cell unit) as coating.This dispersion can comprise carbon black, fluoropolymer and carbon material or graphite granule, and it can also comprise surfactant.Fluoropolymer is calculated by weight with the ratio of carbon black can be in 5/95 to 70/30 scope.These particles can account for 25% to 70% of whole coating weight.The adding of these particles allows to obtain bigger structural intergrity and increases dispersion solid loading, and can not increase viscosity.Therefore, this coating minimizes the crackle in the coating of GDL.
Carbon black is black, amorphous, the carbon element pigment that is produced by the native hydrocarbon thermal decomposition.Usually, three kinds of dissimilar carbon blacks (that is, furnace black, channel black and dim) are arranged.Its common purity (nominalpurity) is about as much as 98.5% to 99.6%.The size of carbon black fine particle can be from 13nm to 95nm.Carbon black can have sphere.
The size of these particles of great majority can be significantly greater than carbon black fine particle.These particles can have the length greater than its diameter.Draw ratio can be between 1.5 to 10000.These particles can comprise that short fiber is as short carbon or graphite fibre, carbon or graphite flake or thin layer, carbon or graphite nanotubes, carbon or graphite fibrillation or carbon or the graphite whisker cut.The diameter of these fibers can be 6 to 20 microns, and length can be 10 to 500 microns.The length of thin slice or thin layer can be 1 to 500 micron.Nanotube, fibrillation and diameter that must be brilliant can be for 5 to 100nm, and its length can be for 5 to the hundreds of micron.Adding these fibers can during drying make mud crack reduce to minimum degree as the compound of coating.
Fig. 2 is shown in the coating on GDL surface, and it comprises chopped carbon fiber.As can be seen from the figure, tangible crackle does not appear in coating.
Except that preventing from coating to form crackle, adding these particles can also increase conductivity in the coating.
The GDL substrate can be made by carbon fibre preform, and it can be a short fiber; Paper; One-way tape; Fabric and nonwoven fabrics comprise looped fabric; And the bonding multi-axial fabric of roll extrusion.Can utilize various technology to apply coating, as dip coated, scrape embrane method, scraper, spraying, roller or slit.
Electrode can be a single bending, can insert adjacent cell.Replacedly, electrode can play single electrode by two two of constituting and linking to each other in a certain way so that connecting.Between electrode, can provide barrier film, can allow ion to pass this barrier film.
Fig. 3 is the schematic diagram of cell of fuel cell 100.Cell of fuel cell 100 can comprise, together with miscellaneous part together, collector electrode 102, gas passage 104, GDL105, catalyst layer 106 and proton exchange membrane 107, its structure is as shown in Figure 3.
Therefore, adding these particles can be reduced in significantly and be the crackle amount in the coating of GDL substrate preparation.Because these particles can make up to 300g/m 2Total coating amount and have the crackle of minimum number.Because the methanol fuel cell unit need be heavier than hydrogen fuel cell unit coating, so said mixture is particularly advantageous in those situations.
Though this paper described in detail preferred embodiment of the present invention with and improve, but be to be understood that, the present invention is not limited to this clear and definite embodiment and improvement, those skilled in the art can carry out other improvement and variation and not depart from thought of the present invention and scope, and it is limited by claims.

Claims (24)

1. coating that is used for the gas diffusion layers of cell of fuel cell or battery, described coating comprises one of carbon black, fluoropolymer and graphite or carbon granule, wherein the size of the described particle of part is significantly greater than described carbon black, and for described coating provides structural intergrity, so that its crackle is reduced to minimum degree.
2. coating according to claim 1, the size of wherein said carbon black fine particle is in the scope of about 13~95nm.
3. coating according to claim 1, wherein said particle is a chopped carbon fiber.
4. coating according to claim 1, wherein said particle are carbon or graphite flake or thin layer.
5. coating according to claim 1, wherein said particle is a carbon nano-tube.
6. coating according to claim 1, wherein said particle is a carbon fibrils.
7. coating according to claim 1, wherein said particle is a carbon whisker.
8. coating according to claim 1, wherein said particle has higher draw ratio.
9. method that is coated with the GDL substrate of cell of fuel cell or battery, described method comprises the steps:
The dispersion of preparation carbon black, fluoropolymer and one of graphite or carbon granule;
Described dispersion is put on described substrate so that be coated with described substrate; And
The size of wherein said particle is significantly greater than described carbon black, and for described coating provides structural intergrity, so that its crackle is reduced to minimum degree.
10. method according to claim 9, the size of wherein said carbon black fine particle is in the scope of about 13~95nm.
11. method according to claim 9, wherein said particle is a chopped carbon fiber.
12. method according to claim 9, wherein said particle are carbon or graphite flake or thin layer.
13. method according to claim 9, wherein said particle is a carbon nano-tube.
14. method according to claim 9, wherein said particle is a carbon fibrils.
15. method according to claim 9, wherein said particle is a carbon whisker.
16. method according to claim 9, wherein said particle has higher draw ratio.
17. goods that are used for cell of fuel cell or battery, described goods are to have the GDL of coating with the substrate of dispersion, wherein said dispersion comprises one of carbon black, fluoropolymer and graphite or carbon granule, wherein the size of the described particle of part is significantly greater than described carbon black, and for described coating provides structural intergrity, so that its crackle is reduced to minimum degree.
18. goods according to claim 17, the size of wherein said carbon black fine particle is in the scope of about 13~95nm.
19. goods according to claim 17, wherein said particle is a chopped carbon fiber.
20. goods according to claim 17, wherein said particle are carbon or graphite flake or thin layer.
21. goods according to claim 17, wherein said particle is a carbon nano-tube.
22. goods according to claim 17, wherein said particle is a carbon fibrils.
23. goods according to claim 17, wherein said particle is a carbon whisker.
24. goods according to claim 17, wherein said particle has higher draw ratio.
CNA2004100960568A 2004-11-26 2004-11-26 Control of micro-craze on carbon coating when preparing GDL electrode layer of fuel cell unit Pending CN1780038A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101662031A (en) * 2008-08-04 2010-03-03 通用汽车环球科技运作公司 Gas diffusion layer with lower gas diffusivity
CN103427099A (en) * 2012-05-16 2013-12-04 通用汽车环球科技运作有限责任公司 Low cost fuel cell diffusion layer configured for optimized anode water management
CN103563143A (en) * 2011-06-17 2014-02-05 日产自动车株式会社 Gas diffusion layer for fuel cell
CN111194497A (en) * 2017-11-29 2020-05-22 东丽株式会社 Microporous layer, method for producing same, gas diffusion electrode substrate, and fuel cell
CN111916762A (en) * 2020-06-30 2020-11-10 中南大学 Diffusion layer of proton exchange membrane fuel cell and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101662031A (en) * 2008-08-04 2010-03-03 通用汽车环球科技运作公司 Gas diffusion layer with lower gas diffusivity
CN103563143A (en) * 2011-06-17 2014-02-05 日产自动车株式会社 Gas diffusion layer for fuel cell
CN103563143B (en) * 2011-06-17 2016-10-26 日产自动车株式会社 Gas diffusion layer for fuel cell
CN103427099A (en) * 2012-05-16 2013-12-04 通用汽车环球科技运作有限责任公司 Low cost fuel cell diffusion layer configured for optimized anode water management
CN111194497A (en) * 2017-11-29 2020-05-22 东丽株式会社 Microporous layer, method for producing same, gas diffusion electrode substrate, and fuel cell
CN111194497B (en) * 2017-11-29 2022-08-09 东丽株式会社 Microporous layer, method for producing same, gas diffusion electrode substrate, and fuel cell
US11621426B2 (en) 2017-11-29 2023-04-04 Toray Industries, Inc. Micro-porous layer and manufacturing method therefor, gas diffusion electrode substrate, and fuel battery
CN111916762A (en) * 2020-06-30 2020-11-10 中南大学 Diffusion layer of proton exchange membrane fuel cell and preparation method thereof

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