CN114293394A - Hydrophobic carbon paper, preparation method thereof, gas diffusion layer and fuel cell - Google Patents
Hydrophobic carbon paper, preparation method thereof, gas diffusion layer and fuel cell Download PDFInfo
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- CN114293394A CN114293394A CN202111679018.5A CN202111679018A CN114293394A CN 114293394 A CN114293394 A CN 114293394A CN 202111679018 A CN202111679018 A CN 202111679018A CN 114293394 A CN114293394 A CN 114293394A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 194
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 67
- 238000009792 diffusion process Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000446 fuel Substances 0.000 title claims abstract description 19
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 109
- 239000007789 gas Substances 0.000 claims abstract description 86
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011737 fluorine Substances 0.000 claims abstract description 48
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 48
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 37
- 239000004917 carbon fiber Substances 0.000 claims abstract description 37
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000012528 membrane Substances 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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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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Abstract
The invention relates to hydrophobic carbon paper and a preparation method thereof, a gas diffusion layer and a fuel cell, wherein the preparation method of the hydrophobic carbon paper comprises the following steps: carrying out surface fluorination treatment on the carbon paper by adopting mixed gas of fluorine gas and nitrogen gas; wherein the carbon paper is compounded by carbon fibers, and the diameter of the carbon fibers is 5-15 mu m; the thickness of the carbon paper is 100-500 μm. The surface fluorination treatment is carried out on the carbon paper with the specific diameter and the specific thickness by adopting the mixed gas of fluorine gas and nitrogen gas, so that the hydrophobic property of the carbon paper is effectively improved, and the conductivity and the porosity are not affected.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to hydrophobic carbon paper, a preparation method thereof, a gas diffusion layer and a fuel cell.
Background
The fuel cell is a device for directly converting chemical energy of hydrogen and oxygen into electric energy through electrode reaction, combustion is not involved in the reaction process, the energy conversion efficiency is not limited by Carnot cycle, and the fuel cell has the remarkable characteristics of high efficiency, cleanness and the like. The proton exchange membrane fuel cell is the fuel cell with the most development potential, has the characteristics of high energy conversion efficiency, environmental friendliness, high specific energy, low operating temperature and quick start, and can be widely applied to the fields of automobiles, ships, fixed power supplies and the like. Gas diffusion layers are the key core materials of proton exchange membrane fuel cells and are typically composed of a substrate layer and a microporous layer. The base material layer is usually made of porous carbon paper, and mainly plays a role in supporting the microporous layer, catalyzing layer, distributing gas and draining water. Therefore, carbon paper used for preparing a gas diffusion layer is generally required to have both high porosity and good electrical conductivity and hydrophobic properties.
The traditional method for enhancing the hydrophobic property of the carbon paper is mainly to arrange a coating containing a conductive agent and a hydrophobic agent on the surface of the carbon paper, so that the hydrophobic treatment of the carbon paper is realized. However, the addition of the conductive agent and the hydrophobic group affects the porosity of the carbon paper, and is not favorable for the transmission of reaction gas and water vapor; and complicated process flows such as dispersion, coating, post-treatment and the like are needed, so that the cost and the resource waste are increased.
Therefore, the preparation method of the hydrophobic carbon paper which has the advantages of porosity, conductivity and hydrophobic property and is simple in process is of great significance.
Disclosure of Invention
Based on the method, the preparation method of the hydrophobic carbon paper, the gas diffusion layer and the fuel cell can effectively improve the hydrophobic performance of the carbon paper, and the conductivity and the porosity are not affected.
The technical scheme of the invention for solving the technical problems is as follows.
A preparation method of hydrophobic carbon paper comprises the steps of carrying out surface fluorination treatment on carbon paper by adopting mixed gas of fluorine gas and nitrogen gas;
the carbon paper is formed by compounding carbon fibers, the diameter of each carbon fiber is 5-15 mu m, and the thickness of the carbon paper is 100-500 mu m.
In some embodiments, in the method for preparing the hydrophobic carbon paper, the volume ratio of the fluorine gas to the nitrogen gas in the mixed gas is 1 (0.01-100).
In some embodiments, in the preparation method of the hydrophobic carbon paper, the volume ratio of the fluorine gas to the nitrogen gas in the mixed gas is 1 (1-10).
In some embodiments, in the preparation method of the hydrophobic carbon paper, the temperature of the surface fluorination treatment is 0-500 ℃ and the time is 0.1-120 min.
In some embodiments, in the preparation method of the hydrophobic carbon paper, the temperature of the surface fluorination treatment is 150-350 ℃ and the time is 10-30 min.
In some embodiments, in the method for preparing the hydrophobic carbon paper, the surface fluorination treatment is performed by placing the carbon paper on a conveyor belt and introducing the carbon paper into a furnace chamber of a fluorination treatment furnace, wherein the furnace chamber comprises an outer chamber and an inner chamber arranged in the outer chamber, the outer chamber is filled with nitrogen, and the inner chamber is filled with a mixed gas of fluorine gas and nitrogen gas.
In some of the embodiments, in the method for preparing the hydrophobic carbon paper, the running speed of the conveyor belt is 0.1m/min to 5.0 m/min.
The invention provides carbon paper which is prepared by adopting the preparation method of the hydrophobic carbon paper.
The invention provides a gas diffusion layer which comprises the carbon paper.
The invention provides a fuel cell, and an electrode of the fuel cell comprises the gas diffusion layer.
Compared with the prior art, the preparation method of the hydrophobic carbon paper has the following beneficial effects:
according to the preparation method of the hydrophobic carbon paper, the mixed gas of fluorine gas and nitrogen gas is adopted to perform surface fluorination treatment on the carbon paper with the specific diameter and the specific thickness, the fluorine gas and the functional groups on the surface of the carbon paper perform fluorine substitution reaction and fluorine addition reaction, and the surface of the carbon paper is fluorinated to a specific degree to form C-F bonds, so that the surface hydrophobicity of the carbon fibers is effectively improved; meanwhile, the carbon paper is made of carbon fiber with a specific diameter and has a specific thickness, so that a C-F bond is not formed in the carbon paper, and the hydrophobic property of the carbon paper is effectively improved and the high conductivity of the carbon paper is maintained under the synergistic effect of the steps and parameters. Moreover, since no hydrophobic agent and conductive agent are used, the porosity of the carbon paper is not affected; and no post-treatment is needed, thereby greatly improving the productivity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a diagram of a fluorination apparatus for performing a surface fluorination treatment of a carbon paper according to an embodiment;
FIG. 2 is an X-ray photoelectron spectrum of the carbon paper prepared in example 1.
Description of reference numerals:
10: a fluorination treatment apparatus; 11: a fluorination treatment furnace; 12: a conveyor belt; 13: a guide roller; 14: a regulating roller; 111: an outer chamber of the fluorination treatment furnace; 112: an inner cavity of the fluorination treatment furnace; 131: a first guide roller; 132: a second guide roller; 20: carbon paper.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element. The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular. "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The inventor of the present application finds, through previous experiments, that the traditional method of providing a coating containing a conductive agent and a hydrophobic agent on the surface of carbon paper affects the porosity of the carbon paper, and is not beneficial to the transmission of reaction gas and water vapor, and therefore, the discovery of a method for preparing hydrophobic carbon paper without using a conductive agent and a hydrophobic agent is the first step of ensuring the porosity of the carbon paper. The inventor finds that the carbon paper is subjected to surface fluorination treatment by using the mixed gas of fluorine gas and nitrogen gas, and the specific diameter carbon fiber material and the thickness of the carbon paper are limited, so that the hydrophobic property of the carbon paper is effectively improved, and the high conductivity and porosity of the carbon paper are maintained.
In the research, the surface fluorination treatment is carried out on the carbon paper only by fluorine gas, and the carbon fiber in the carbon paper is easily etched, so that the porosity is increased; or other carbon fiber materials with smaller diameter or thinner carbon paper are adopted, and the perfluorocarbon material is easy to obtain by violent reaction in the fluorination process, so that the electric conductivity is obviously reduced.
One embodiment of the invention provides a preparation method of hydrophobic carbon paper, which comprises the steps of carrying out surface fluorination treatment on carbon paper by adopting mixed gas of fluorine gas and nitrogen gas;
wherein the carbon paper is compounded by carbon fibers, the diameter of the carbon fibers is 5-15 mu m, and the thickness of the carbon paper is 100-500 mu m.
The surface fluorination treatment is carried out on the carbon paper with a specific diameter and a specific thickness by adopting the mixed gas of fluorine gas and nitrogen gas, the fluorine gas and the functional groups on the surface of the carbon paper carry out fluorine substitution reaction and fluorine addition reaction, the surface of the carbon paper is fluorinated to a specific degree to form C-F bonds, and the surface hydrophobicity of the carbon fiber is effectively improved; meanwhile, the carbon paper is made of carbon fiber with a specific diameter and has a specific thickness, so that a C-F bond is not formed in the carbon paper, and the hydrophobic property of the carbon paper is effectively improved and the high conductivity of the carbon paper is maintained under the synergistic effect of the steps and parameters. Moreover, since no hydrophobic agent and conductive agent are used, the porosity of the carbon paper is not affected; and no post-treatment is needed, thereby greatly improving the productivity.
It is understood that the carbon fibers may have diameters of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm; the thickness of the carbon paper may be 100 μm, 110 μm, 120 μm, 150 μm, 180 μm, 200 μm, 220 μm, 235 μm, 260 μm, 300 μm, 350 μm, 400 μm, 500 μm, or the like.
In some examples, the hydrophobic carbon paper is prepared by a method in which carbon fibers have a diameter of 7 to 10 μm; optionally, the carbon fibers have a diameter of 8 μm.
In some examples, the hydrophobic carbon paper is prepared by a method in which the carbon paper has a thickness of 100 to 400 μm; optionally, the carbon paper has a thickness of 200 μm.
In some examples, in the preparation method of the hydrophobic carbon paper, the volume ratio of fluorine gas to nitrogen gas in the mixed gas is 1 (0.01-100); further, the volume ratio of the fluorine gas to the nitrogen gas is 1 (1-20); optionally, the volume ratio of the fluorine gas to the nitrogen gas is 1 (1-10).
In some preferred examples, in the method for preparing the hydrophobic carbon paper, the volume ratio of fluorine gas to nitrogen gas in the mixed gas is 1: 4.
By controlling the volume ratio of the fluorine gas to the nitrogen gas, the control of the rate of the fluorination reaction and the accurate control of the fluorine content are facilitated.
In some examples, in the preparation method of the hydrophobic carbon paper, the temperature of the surface fluorination treatment is 0-500 ℃, and the time is 0.1 min-2 h; further, the temperature of the surface fluorination treatment is 100-400 ℃; optionally, the temperature of the surface fluorination treatment is 150 ℃ to 350 ℃.
In some preferred examples, the hydrophobic carbon paper is prepared by a process wherein the surface fluorination treatment is carried out at a temperature of 250 ℃.
By controlling the size of the carbon paper, the volume ratio of fluorine gas to nitrogen gas, and the temperature and time of the surface fluorination treatment, the fluorine-carbon ratio of the carbon paper can be controlled, so that the fluorination degree of the carbon paper can be controlled.
In some examples, the hydrophobic carbon paper is prepared by placing the carbon paper on a conveyor belt and introducing the carbon paper into a furnace chamber of a fluorination furnace, wherein the furnace chamber comprises an outer chamber and an inner chamber arranged in the outer chamber, the outer chamber is filled with nitrogen, and the inner chamber is filled with a mixed gas of fluorine and nitrogen.
Referring to fig. 1, in some specific examples of the method for manufacturing the hydrophobic carbon paper, a fluorination treatment apparatus 10 for performing a surface fluorination treatment on the carbon paper includes a fluorination treatment furnace 11, a conveyor belt 12, a guide roller 13, and a dancer roller 14.
Wherein, the furnace chamber of the fluorination treatment furnace 11 comprises an outer chamber 111 and an inner chamber 112 arranged in the outer chamber 111. The outer chamber 111 is filled with nitrogen gas, and the inner chamber 112 is filled with a mixed gas of fluorine gas and nitrogen gas. Further, the outer cavity 111 completely surrounds the inner cavity 112, in other words, an annular cavity is formed between the outer wall of the inner cavity 112 and the inner wall of the outer cavity 111. An annular cavity is formed between the outer wall of the inner cavity 112 and the inner wall of the outer cavity 111, and the outer cavity 111 is filled with nitrogen, so that fluorine gas in the inner cavity 112 at the place where fluorine substitution reaction and fluorine addition reaction occur is prevented from leaking.
The guide roller 13 includes a first guide roller 131 and a second guide roller 132, the first guide roller 131 and the second guide roller 132 are respectively provided at both ends of the conveyor belt 12 for guiding the movement of the conveyor belt 12, and the fluorination treatment furnace 11 is provided between the first guide roller 131 and the second guide roller 132.
The carbon paper 20 is placed on the conveyor belt 12, and the carbon paper 20 enters the fluorination treatment furnace 11 from the side where the first guide roller 131 is located along with the operation of the conveyor belt 12 to be subjected to surface fluorination treatment, and is then sent out from the side where the second guide roller 132 is located, so that the hydrophobic carbon paper subjected to surface fluorination treatment is obtained.
In the conventional fluorination treatment, the reaction is carried out in a closed space in order to prevent leakage of fluorine gas. By adopting the fluorination treatment device 10 to perform surface fluorination treatment on the carbon paper, the outer cavity 111 is filled with nitrogen, so that the flow of the external air and the gas of the inner cavity 112 is blocked, the fluorination treatment is not required to be performed in a closed space, and the operation environment is simple.
In some of these examples, the hydrophobic carbon paper is produced by a method wherein the conveyor belt 12 is run at a speed of 0.1m/min to 5.0 m/min.
It can be understood that the running speed of the conveyor belt 12 is adjusted according to the running distance of the conveyor belt 12 in the inner cavity 112 of the fluorination treatment furnace 11, it is further understood that the running distance of the conveyor belt 12 in the inner cavity 112 of the fluorination treatment furnace 11 is the length of the inner cavity 112 of the fluorination treatment furnace 11, and when the length of the inner cavity 112 is fixed, the running speed of the conveyor belt 12 is controlled to determine the time for performing the surface fluorination treatment on the carbon paper.
In some specific examples, in the preparation method of the hydrophobic carbon paper, the length of an inner furnace 112 in the fluorination treatment furnace 11 is 0.5-12 m; further, the running speed of the conveyor belt 12 is 0.1m/min to 5.0 m/min; optionally, the running speed of the conveyor belt 12 is 0.4m/min to 1.2 m/min; preferably, the running speed of the conveyor belt 12 is 1.0 m/min.
The size of the carbon paper, the volume ratio of fluorine gas to nitrogen gas, the temperature of surface fluorination treatment, the running speed of the conveyor belt and the like are controlled, so that the fluorine-carbon ratio of the carbon paper can be controlled, and the fluorination degree of the carbon paper can be controlled.
In some examples, in the method for preparing the hydrophobic carbon paper, before the carbon paper 20 enters the fluorination treatment furnace 11, nitrogen is introduced to remove the air in the outer cavity 111 and the inner cavity 112 of the fluorination treatment furnace 11, and then the fluorination treatment furnace 11 is kept at the temperature of 0-500 ℃.
Before the surface fluorination treatment of the carbon paper, the air in the outer cavity 111 and the inner cavity 112 of the fluorination treatment furnace 11 is removed in advance, so as to prevent the carbon paper from being oxidized by the oxygen in the air after entering.
The invention provides carbon paper, which is prepared by the preparation method of the hydrophobic carbon paper.
An embodiment of the invention provides an application of the carbon paper in preparing a gas diffusion layer. Another embodiment of the present invention provides a gas diffusion layer, which is made of the carbon paper.
The carbon paper is used for preparing the gas diffusion layer, can endow the gas diffusion layer with better hydrophobic property and electrical conductivity, and has higher porosity.
In some of these embodiments, the gas diffusion layer comprises the carbon paper described above, i.e., the gas diffusion layers are all the carbon papers described above. In other embodiments, the gas diffusion layer may include other materials in addition to the carbon paper described above.
An embodiment of the present invention provides a membrane-electrode assembly comprising a catalyst coated membrane and the above-described gas diffusion layer. It can be understood that the catalyst coating film comprises an anode catalyst layer, a cathode catalyst layer and a proton exchange membrane, the anode catalyst layer and the cathode catalyst layer are respectively sprayed on two sides of the proton exchange membrane, and gas diffusion layers are respectively arranged on the sides, far away from the proton exchange membrane, of the anode catalyst layer and the cathode catalyst layer in the catalyst coating film.
The invention provides a fuel cell, which comprises an anode plate, a cathode plate and the membrane electrode assembly, wherein the anode plate and the cathode plate are arranged on two sides of the membrane electrode assembly.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Hereinafter, the hydrophobic carbon paper and the method of preparing the same, the gas diffusion layer, and the fuel cell according to the present invention are exemplified, and it is understood that the hydrophobic carbon paper and the method of preparing the same, the gas diffusion layer, and the fuel cell according to the present invention are not limited to the following examples.
Example 1
Preparing materials: the length of the inner cavity of the fluorination treatment furnace is 10 m; the carbon paper comprises carbon fibers, wherein the diameter of the carbon fibers in the carbon paper is 8 micrometers, and the thickness of the carbon paper is 200 micrometers;
introducing nitrogen to remove air in the inner cavity and the outer cavity of the fluorination treatment furnace, and heating the fluorination treatment furnace to 250 ℃ for heat preservation; placing the carbon paper on a uniform-speed conveyor belt, wherein the running speed of the conveyor belt is 1.0m/min, feeding the carbon paper into a fluorination treatment furnace through the conveyor belt, and simultaneously introducing mixed gas of fluorine gas and nitrogen gas with the volume ratio of 1:4 into an inner cavity of the fluorination treatment furnace to perform surface fluorination treatment on the carbon paper; and (4) along with the movement of the conveyor belt, sending out the carbon paper with the surface fluorinated from the other end of the equipment to obtain the hydrophobic carbon paper.
Example 2
Preparing materials: the length of the inner cavity of the fluorination treatment furnace is 12 m; the carbon paper comprises carbon fibers, wherein the diameter of the carbon fibers in the carbon paper is 15 micrometers, and the thickness of the carbon paper is 400 micrometers;
introducing nitrogen to remove air in the inner cavity and the outer cavity of the fluorination treatment furnace, and heating the fluorination treatment furnace to 100 ℃ for heat preservation; placing the carbon paper on a uniform-speed conveyor belt, wherein the running speed of the conveyor belt is 0.2m/min, feeding the carbon paper into a fluorination treatment furnace through the conveyor belt, and simultaneously introducing mixed gas of fluorine gas and nitrogen gas with the volume ratio of 1:10 into an inner cavity of the fluorination treatment furnace to perform surface fluorination treatment on the carbon paper; and (4) along with the movement of the conveyor belt, sending out the carbon paper with the surface fluorinated from the other end of the equipment to obtain the hydrophobic carbon paper.
Example 3
Preparing materials: the length of the inner cavity of the fluorination treatment furnace is 0.5 m; the carbon paper comprises carbon fibers, wherein the diameter of the carbon fibers in the carbon paper is 5 micrometers, and the thickness of the carbon paper is 100 micrometers;
introducing nitrogen to remove air in the inner cavity and the outer cavity of the fluorination treatment furnace, and heating the fluorination treatment furnace to 350 ℃ for heat preservation; placing the carbon paper on a uniform-speed conveyor belt, wherein the running speed of the conveyor belt is 0.1m/min, feeding the carbon paper into a fluorination treatment furnace through the conveyor belt, and simultaneously introducing mixed gas of fluorine gas and nitrogen gas with the volume ratio of 1:1 into an inner cavity of the fluorination treatment furnace to perform surface fluorination treatment on the carbon paper; and (4) along with the movement of the conveyor belt, sending out the carbon paper with the surface fluorinated from the other end of the equipment to obtain the hydrophobic carbon paper.
Example 4
Preparing materials: the length of the inner cavity of the fluorination treatment furnace is 8 m; the carbon paper comprises carbon fibers, wherein the diameter of the carbon fibers in the carbon paper is 8 micrometers, and the thickness of the carbon paper is 300 micrometers;
introducing nitrogen to remove air in the inner cavity and the outer cavity of the fluorination treatment furnace, and heating the fluorination treatment furnace to 300 ℃ for heat preservation; placing the carbon paper on a uniform-speed conveyor belt, wherein the running speed of the conveyor belt is 0.4m/min, feeding the carbon paper into a fluorination treatment furnace through the conveyor belt, and simultaneously introducing mixed gas of fluorine gas and nitrogen gas with the volume ratio of 1:5 into an inner cavity of the fluorination treatment furnace to perform surface fluorination treatment on the carbon paper; and (4) along with the movement of the conveyor belt, sending out the carbon paper with the surface fluorinated from the other end of the equipment to obtain the hydrophobic carbon paper.
Example 5
Preparing materials: the length of the inner cavity of the fluorination treatment furnace is 10 m; the carbon paper comprises carbon fibers, wherein the diameter of the carbon fibers in the carbon paper is 10 micrometers, and the thickness of the carbon paper is 200 micrometers;
introducing nitrogen to remove air in the inner cavity and the outer cavity of the fluorination treatment furnace, and heating the fluorination treatment furnace to 500 ℃ for heat preservation; placing the carbon paper on a uniform-speed conveyor belt, wherein the running speed of the conveyor belt is 5m/min, feeding the carbon paper into a fluorination treatment furnace through the conveyor belt, and simultaneously introducing mixed gas of fluorine gas and nitrogen gas with the volume ratio of 1:9 into an inner cavity of the fluorination treatment furnace to perform surface fluorination treatment on the carbon paper; and (4) along with the movement of the conveyor belt, sending out the carbon paper with the surface fluorinated from the other end of the equipment to obtain the hydrophobic carbon paper.
Example 6
Preparing materials: the length of the inner cavity of the fluorination treatment furnace is 12 m; the carbon paper comprises carbon fibers, wherein the diameter of the carbon fibers in the carbon paper is 7 micrometers, and the thickness of the carbon paper is 200 micrometers;
introducing nitrogen to remove air in the inner cavity and the outer cavity of the fluorination treatment furnace, and heating the fluorination treatment furnace to 0 ℃ for heat preservation; placing the carbon paper on a uniform-speed conveyor belt, wherein the running speed of the conveyor belt is 0.1m/min, conveying the carbon paper into a fluorination treatment furnace through the conveyor belt, and simultaneously introducing mixed gas of fluorine gas and nitrogen gas with the volume ratio of 1:20 into an inner cavity of the fluorination treatment furnace to perform surface fluorination treatment on the carbon paper; and (4) along with the movement of the conveyor belt, sending out the carbon paper with the surface fluorinated from the other end of the equipment to obtain the hydrophobic carbon paper.
Comparative example 1
60g of graphitized carbon powder serving as a conductive agent is subjected to slurry dispersion, then 40g of polytetrafluoroethylene solution (60% mass fraction aqueous solution) is added into the mixture by using mechanical stirring, and a thickening agent is added to adjust the viscosity of the mixture, so that the carbon concentration in the final slurry is 2.5-4%; coating the prepared slurry on carbon paper, and carrying out heat treatment at 300 ℃ to obtain the hydrophobic carbon paper.
Comparative example 2
Preparing materials: the length of the inner cavity of the fluorination treatment furnace is 10 m; the carbon paper comprises carbon fibers, wherein the diameter of the carbon fibers in the carbon paper is 8 micrometers, and the thickness of the carbon paper is 200 micrometers;
introducing nitrogen to remove air in the inner cavity and the outer cavity of the fluorination treatment furnace, and heating the fluorination treatment furnace to 250 ℃ for heat preservation; placing the carbon paper on a uniform-speed conveyor belt, wherein the running speed of the conveyor belt is 1.0m/min, conveying the carbon paper into a fluorination treatment furnace through the conveyor belt, and simultaneously introducing fluorine gas into an inner cavity of the fluorination treatment furnace to perform surface fluorination treatment on the carbon paper; and (4) along with the movement of the conveyor belt, sending out the carbon paper with the surface fluorinated from the other end of the equipment to obtain the hydrophobic carbon paper.
Comparative example 3
Preparing materials: the length of the inner cavity of the fluorination treatment furnace is 10 m; the carbon paper comprises carbon fibers, wherein the diameter of the carbon fibers in the carbon paper is 2 micrometers, and the thickness of the carbon paper is 10 micrometers;
introducing nitrogen to remove air in the inner cavity and the outer cavity of the fluorination treatment furnace, and heating the fluorination treatment furnace to 250 ℃ for heat preservation; placing the carbon paper on a uniform-speed conveyor belt, wherein the running speed of the conveyor belt is 1.0m/min, feeding the carbon paper into a fluorination treatment furnace through the conveyor belt, and simultaneously introducing mixed gas of fluorine gas and nitrogen gas with the volume ratio of 1:4 into an inner cavity of the fluorination treatment furnace to perform surface fluorination treatment on the carbon paper; and (4) along with the movement of the conveyor belt, sending out the carbon paper with the surface fluorinated from the other end of the equipment to obtain the hydrophobic carbon paper.
The condition parameters of each example and comparative example are shown in table 1, wherein the thickness refers to the thickness of the carbon paper, the diameter refers to the diameter of carbon fibers in the carbon paper, F2:N2The volume ratio of fluorine gas to nitrogen gas introduced in the surface fluorination treatment process is referred to, the temperature refers to the temperature of the surface fluorination treatment, and the running speed refers to the running speed of the conveyor belt.
TABLE 1
The hydrophobic carbon papers prepared in the respective examples and comparative examples were tested for their surface fluorine to carbon ratio by X-ray photoelectron spectroscopy (XPS), and the results are shown in table 2.
The hydrophobic carbon paper prepared in each example and comparative example was subjected to a water contact angle test, a through plane reactive test and a porosity test, and the test results are shown in table 2.
TABLE 2
As can be seen from table 2, compared with comparative proportions of 1 to 3, the hydrophobic carbon papers obtained in examples 1 to 6 have better hydrophobic property, and the conductivity and the porosity are basically not affected; while comparative example 1, which employs conductive additives and hydrophobic agents, results in a decrease in porosity, which affects the gas diffusion rate, although both hydrophobicity and conductivity meet the fuel cell requirements; compared with the example 1, the fluorine gas content is too high, which causes the fluorination reaction rate to be too fast, and the fluorine-carbon ratio is too high, which finally causes the resistance to be too high; furthermore, since the fluorination reaction is too violent, the carbon fibers are etched, causing an increase in porosity; the diameter and thickness of the carbon fiber in comparative example 3, which are out of the specified ranges, result in a rapid increase in fluorine content, while the increase in surface fluorine element after fluorination causes an increase in porosity and electrical resistance of the carbon paper.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (10)
1. The preparation method of the hydrophobic carbon paper is characterized by comprising the following steps:
carrying out surface fluorination treatment on the carbon paper by adopting mixed gas of fluorine gas and nitrogen gas;
the carbon paper is formed by compounding carbon fibers, the diameter of each carbon fiber is 5-15 mu m, and the thickness of the carbon paper is 100-500 mu m.
2. The method according to claim 1, wherein the volume ratio of the fluorine gas to the nitrogen gas in the mixed gas is 1 (0.01 to 100).
3. The method according to claim 2, wherein the volume ratio of the fluorine gas to the nitrogen gas in the mixed gas is 1 (1-10).
4. The method according to claim 1, wherein the surface fluorination treatment is carried out at a temperature of 0 ℃ to 500 ℃ for a time of 0.1min to 120 min.
5. The method according to claim 4, wherein the surface fluorination treatment is carried out at a temperature of 150 to 350 ℃ for 10 to 30 minutes.
6. The process according to any one of claims 1 to 5, wherein the surface fluorination treatment is carried out by placing the carbon paper on a conveyor belt and introducing the carbon paper into a furnace chamber of a fluorination treatment furnace, the furnace chamber comprising an outer chamber and an inner chamber provided in the outer chamber, the outer chamber being filled with nitrogen gas, and the inner chamber being filled with a mixed gas of fluorine gas and nitrogen gas.
7. The method of claim 6, wherein the conveyor belt is operated at a speed of 0.1m/min to 5.0 m/min.
8. The hydrophobic carbon paper is characterized by being prepared by the preparation method of the hydrophobic carbon paper according to any one of claims 1 to 7.
9. A gas diffusion layer comprising the hydrophobic carbon paper of claim 8.
10. A fuel cell, characterized in that the electrode of the fuel cell comprises a gas diffusion layer according to claim 9.
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