CN114597428A - Flexible carbon paper, preparation method thereof, gas diffusion layer and fuel cell - Google Patents
Flexible carbon paper, preparation method thereof, gas diffusion layer and fuel cell Download PDFInfo
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- CN114597428A CN114597428A CN202210240051.6A CN202210240051A CN114597428A CN 114597428 A CN114597428 A CN 114597428A CN 202210240051 A CN202210240051 A CN 202210240051A CN 114597428 A CN114597428 A CN 114597428A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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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
Abstract
The invention relates to flexible carbon paper, a preparation method thereof, a gas diffusion layer and a fuel cell. The carbon film is formed on the surface of the carbon-based paper by adopting a chemical vapor deposition method and a specific carbon-containing precursor, carbon atoms generated by pyrolysis of the carbon-containing precursor collide and react to form the carbon film, and meanwhile, chlorine atoms in the carbon-containing precursor can effectively promote sp3The formation of hybridized carbon atoms plays a role in inducing crosslinking on the structure of the carbon film formed by deposition to form a three-dimensional crosslinking structure, so that the formed carbon film has better flexibility and higher conductivity, and the flexible carbon paper with excellent conductivity is prepared.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to flexible 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 a fuel cell with the most development potential, has the characteristics of high energy conversion efficiency, environmental friendliness, high specific energy, low operation 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 carbon paper is a common gas diffusion layer substrate material, has a uniform porous thin layer structure, and is high in mechanical strength and electrical conductivity, and good in chemical stability and thermal stability. However, carbon paper is brittle, lacks flexibility, is easily damaged and broken during the process of preparing electrodes, is not conducive to large-scale continuous industrial production and transportation, and directly affects the overall life of fuel cells.
The traditional method for treating the carbon paper in a flexible way is to perform primary treatment by adopting a silane coupling agent and zinc oxide with a four-needle shape and then spray polytetrafluoroethylene to form a surface layer with flexibility. However, the zinc oxide introduced by the method can cause the precipitation of zinc ions during the use process of the fuel cell, so that the catalyst of the fuel cell is disabled; meanwhile, the conductive performance of the carbon paper is reduced due to the introduction of low-conductivity substances such as silane coupling agents, zinc oxide, polytetrafluoroethylene and the like into the surface of the carbon paper.
Therefore, the flexible carbon paper capable of effectively improving the flexibility and enhancing the conductivity and the preparation method thereof have important significance.
Disclosure of Invention
Based on the carbon paper, the invention provides the flexible carbon paper which can effectively improve the flexibility and enhance the conductivity, the preparation method thereof, the gas diffusion layer and the fuel cell.
The technical scheme of the invention for solving the technical problems is as follows.
The flexible carbon paper comprises carbon-based paper and a carbon film, wherein the carbon film is deposited on the surface of the carbon-based paper by adopting a chemical vapor deposition method, and a carbon-containing precursor used in the chemical vapor deposition method contains chlorinated organic matters.
In some of these embodiments, the chlorinated organic is at least one of chlorinated aromatic compounds and chlorinated C1-C4 alkanes in the flexible carbon paper.
In some of these embodiments, the chlorinated organic is selected from at least one of chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, dichloromethane, trichloromethane, tetrachloromethane, and 1, 2-dichloroethane in the flexible carbon paper.
In some of these embodiments, the flexible carbon paper further includes a non-chlorinated organic in the carbon-containing precursor.
In some of these embodiments, the non-chlorinated organic is selected from at least one of ethanol, ethyl acetate, and toluene in the flexible carbon paper.
In some embodiments, the volume ratio of the chlorinated organic compound to the non-chlorinated organic compound in the chemical vapor deposition is 1 (0.1-10).
The invention provides a preparation method of flexible carbon paper, which comprises the following steps:
and depositing a carbon film on the surface of the carbon-based paper by adopting a chemical vapor deposition method.
In some embodiments, in the preparation method of the flexible carbon paper, the reaction temperature in the chemical vapor deposition is 900-1200 ℃, and the reaction time is 0.5-120 min.
In some of these embodiments, the method of making a flexible carbon paper, the chemical vapor deposition comprises the steps of:
and introducing the carbon-based paper into a furnace chamber of a chemical vapor deposition furnace by adopting a conveyor belt for chemical vapor deposition, wherein the furnace chamber comprises an outer cavity and an inner cavity arranged in the outer cavity, nitrogen or argon is filled into the outer cavity, and the carbon-containing precursor is filled into the inner cavity for deposition.
The invention provides a gas diffusion layer which comprises the flexible 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 flexible carbon paper has the following beneficial effects:
the flexible carbon paper comprises carbon-based paper and a carbon film, wherein the carbon film is deposited on the surface of the carbon-based paper by adopting a chemical vapor deposition method, and a carbon-containing precursor used in the chemical vapor deposition comprises chlorinated organic matters; the carbon film is formed on the surface of the carbon-based paper by adopting a chemical vapor deposition method and a specific carbon-containing precursor, carbon atoms generated by pyrolysis of the carbon-containing precursor collide and react to form the carbon film, and meanwhile, chlorine atoms in the carbon-containing precursor can effectively promote sp3The formation of hybridized carbon atoms plays a role in inducing crosslinking on the structure of the carbon film formed by deposition to form a three-dimensional crosslinking structure, so that the formed carbon film has better flexibility and higher conductivity, and the flexible carbon paper with excellent conductivity is prepared.
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 an apparatus for manufacturing a flexible carbon paper according to an example.
Description of reference numerals:
10. a device for preparing flexible carbon paper; 11. a chemical vapor deposition furnace; 111. an outer cavity; 112. an inner cavity; 12. a conveyor belt; 13. a guide roller; 131. a first guide roller; 132 a second guide roller; 14. a regulating roller; 15. an air inlet pipe; 16. an air outlet pipe; 20. carbon-based paper.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. It is to be understood that these embodiments are provided so that this disclosure will be thorough and complete.
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.
In the description of the present invention, "a plurality" means two or more unless specifically defined 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.
One embodiment of the invention provides flexible carbon paper, which comprises carbon-based paper and a carbon film, wherein the carbon film is deposited on the surface of the carbon-based paper by adopting a chemical vapor deposition method, and a carbon-containing precursor used in the chemical vapor deposition comprises chlorinated organic matters.
The carbon film is formed on the surface of the carbon-based paper by adopting a chemical vapor deposition method and a specific carbon-containing precursor, carbon atoms generated by pyrolysis of the carbon-containing precursor collide and react to form the carbon film on the inner pore surface and the outer surface of the carbon-based paper taking the carbon fiber as a network structure, and chlorine atoms in the carbon-containing precursor can effectively promote sp (sp) atoms3The formation of hybridized carbon atoms plays a role in inducing crosslinking on the structure of the carbon film formed by deposition to form a three-dimensional crosslinking structure, so that the formed carbon film has better flexibility and higher conductivity, and the flexible carbon paper with excellent conductivity is prepared. The carbon film is coated on the surface of the carbon-based paper to form an interconnected coating structure, the carbon fiber is fixed, and the carbon paper is bentWhen the stress is applied, the bending stress is absorbed by the carbon film with flexibility, so that the carbon paper has bending deformation capable of keeping larger. The carbon paper with better flexibility is more beneficial to processing and manufacturing, can improve the processing performance and the anti-damage capability of the surface of the material, prolongs the service life of the material, intensifies the shape of the carbon electrode product, and effectively reduces the packaging and transportation cost.
In some examples, the chlorinated organic compound is at least one of chlorinated aromatic compound and chlorinated C1-C4 alkane.
In some of these examples, the chlorinated organic is selected from at least one of chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, dichloromethane, trichloromethane, tetrachloromethane, and 1, 2-dichloroethane in the flexible carbon paper. Optionally, the chlorinated organic is selected from at least one of chlorobenzene, o-dichlorobenzene, trichloromethane and tetrachloromethane.
In some specific examples, the chlorinated organic is selected from chlorobenzene, o-dichlorobenzene, trichloromethane and tetrachloromethane. Further, the chlorinated organic is selected from chlorobenzene or trichloromethane.
In some preferred examples, the chlorinated organic is chloroform in the flexible carbon paper.
By controlling the type of the carbon-containing precursor, the flexibility of the carbon film can be adjusted, so that the flexibility of the carbon paper is enhanced.
In some of these examples, the carbon-containing precursor in the flexible carbon paper further comprises a non-chlorinated organic.
In some of these examples, the non-chlorinated organic is selected from at least one of ethanol, ethyl acetate, and toluene in the flexible carbon paper.
In some specific examples, the organic material in the flexible carbon paper is ethanol.
In some examples, the volume ratio of chlorinated organic compounds to non-chlorinated organic compounds in the flexible carbon paper in chemical vapor deposition is 1 (0.1-10). It is understood that the volume ratio of chlorinated organics to non-chlorinated organics can be 1:0.1, 1:0.5, 1:1, 1:2, 1:3, 1:5, 1:8, 1: 10.
Furthermore, the volume ratio of chlorinated organic compounds to non-chlorinated organic compounds is 1 (0.5-3); optionally, the volume ratio of the chlorinated organic compound to the non-chlorinated organic compound is 1 (0.5-1); preferably, the volume ratio of chlorinated organics to non-chlorinated organics is 1: 1.
Adding a non-chlorinated organic compound into the carbon-containing precursor to serve as a carbon source and play a role in diluting the chlorinated organic compound; the volume ratio of chlorinated organic compounds to non-chlorinated organic compounds is further controlled, and the influence of the generated carbon film on the porosity of the carbon paper can be further reduced.
One embodiment of the present invention provides a method for preparing flexible carbon paper, comprising the steps of:
and depositing a carbon film on the surface of the carbon-based paper by adopting a chemical vapor deposition method.
In some examples, the flexible carbon paper is prepared by a chemical vapor deposition method, wherein the reaction temperature is 900-1200 ℃ and the reaction time is 0.5-120 min. It is understood that the reaction temperature in chemical vapor deposition may be 900 deg.C, 920 deg.C, 950 deg.C, 980 deg.C, 1000 deg.C, 1020 deg.C, 1050 deg.C, 1070 deg.C, 1090 deg.C, 1100 deg.C, 1120 deg.C, 1135 deg.C, 1150 deg.C, 1178 deg.C, 1196 deg.C, 1200 deg.C, etc., and the reaction time may be 0.5min, 1min, 5min, 10min, 20min, 30min, 40min, 50min, 70min, 85min, 88min, 90min, 95min, 98min, 100min, 120min, etc.
Optionally, the reaction temperature in the chemical vapor deposition is 900-1100 ℃; further, the reaction temperature in chemical vapor deposition is 1000 ℃ to 1100 ℃.
In some specific examples, the reaction temperature in chemical vapor deposition is 1100 ℃ in the method for making the flexible carbon paper.
In some examples, the method of making the flexible carbon paper comprises the steps of:
and introducing the carbon-based paper into a furnace chamber of a chemical vapor deposition furnace by adopting a conveyor belt for chemical vapor deposition, wherein the furnace chamber comprises an outer chamber and an inner chamber arranged in the outer chamber, nitrogen or argon is filled into the outer chamber, and the carbon-containing precursor is filled into the inner chamber for deposition.
Referring to fig. 1, in some specific examples, in a method for manufacturing a flexible carbon paper, a manufacturing apparatus 10 for a flexible carbon paper includes a chemical vapor deposition furnace 11, a conveyor belt 12, a guide roller 13, and a regulation roller 14.
Wherein the chamber of the chemical vapor deposition furnace 11 comprises an outer chamber 111 and an inner chamber 112 disposed in the outer chamber 111. The outer chamber 111 is filled with nitrogen or argon. Further, the chemical vapor deposition furnace 11 further includes an inlet pipe 15 and an outlet pipe 16, the carbon-containing precursor is injected into the inner cavity 112 from the inlet pipe 15, and the tail gas in the chemical vapor deposition is discharged from the tail gas pipe 16 and then is treated. It will be appreciated that both inlet tube 15 and outlet tube 16 pass through outer chamber 111 and inner chamber 112. 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 or argon, so that chlorine-containing gas generated during the cracking of the carbon-containing precursor is prevented from leaking into the air.
The guide rollers 13 include a first guide roller 131 and a second guide roller 132, the first guide roller 131 and the second guide roller 132 are respectively disposed at both ends of the conveyor belt 12 for guiding the movement of the conveyor belt 12, and the chemical vapor deposition furnace 11 is disposed between the first guide roller 131 and the second guide roller 132.
The carbon-based paper 20 is placed on the conveyor belt 12, the carbon-based paper 20 runs along with the conveyor belt 12, enters the chemical vapor deposition furnace 11 from the side where the first guide roller 131 is located, and is sent out from the side where the second guide roller 132 is located after a carbon film is formed on the surface of the carbon-based paper, and then the flexible carbon paper is obtained.
In some of these examples, the flexible carbon paper is produced by a method wherein the conveyor belt 12 is run at a speed of 0.1m/min to 10 m/min. It is understood that the speed of the conveyor belt 12 can be 0.1m/min, 0.5m/min, 1m/min, 2m/min, 3m/min, 5m/min, 6m/min, 8m/min, 10m/min, etc.
In some preferred examples, the flexible carbon paper is produced by a method wherein the conveyor belt 12 is run at a speed of 1 m/min.
In some examples, the carbon-containing precursor is injected at a rate of 2mL/min to 10mL/min in the method for preparing the flexible carbon paper. It is understood that the injection rate of the carbon-containing precursor can be 2mL/min, 2.5mL/min, 3mL/min, 4mL/min, 5mL/min, 6mL/min, 8mL/min, 9mL/min, 10mL/min, and the like. Optionally, the injection speed of the carbon-containing precursor is 2mL/min to 8 mL/min.
In some preferred examples, the carbon-containing precursor is injected at a rate of 5mL/min during the process of making the flexible carbon paper.
It is understood that the time for the carbon film to grow depends on the running speed of the conveyor belt 12 and the length of the cavity 112 in the chemical vapor deposition furnace 11, and when the length of the cavity 112 is fixed, the time for the carbon film to grow can be determined by controlling the running speed of the conveyor belt 12. The growth rate of the carbon film can be controlled by controlling the time for depositing the carbon film on the surface of the carbon paper, the injection speed of the carbon-containing precursor, the temperature of chemical vapor deposition and the like, so that the thickness of the carbon film deposited on the surface of the carbon-based paper can be regulated and controlled.
In some specific examples, the flexible carbon paper is prepared by a method in which the length of the inner cavity 112 is 5m to 20 m.
In some examples, in the method for preparing the flexible carbon paper, before the step of introducing the carbon-based paper 20 into the chemical vapor deposition furnace 11, nitrogen or argon is introduced in advance to remove air in the outer cavity 111 and the inner cavity 112 of the chemical vapor deposition furnace 11, and then the chemical vapor deposition furnace 11 is maintained at 900 ℃ to 1200 ℃.
Before the carbon film is deposited on the surface of the carbon-based paper, the air in the outer chamber 111 and the inner chamber 112 of the chemical vapor deposition furnace 11 is removed in advance, so as to prevent the carbon-based paper from being oxidized by the oxygen in the air.
An embodiment of the present invention provides an application of the above flexible carbon paper in preparing a gas diffusion layer. In another embodiment of the present invention, a gas diffusion layer is provided, and the material of the gas diffusion layer includes the flexible carbon paper. Further, the gas diffusion layer comprises a substrate layer and a microporous layer, and the material of the substrate layer comprises the flexible carbon paper.
The flexible carbon paper is used for preparing the gas diffusion layer, and has good flexibility, strong electric conductivity and high porosity.
In some of these embodiments, the gas diffusion layer comprises the above-described flexible carbon paper, i.e., the gas diffusion layers are all the above-described flexible carbon paper. In other embodiments, the gas diffusion layer may comprise other materials in addition to the flexible 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 flexible carbon paper and the method of manufacturing the same, the gas diffusion layer, and the fuel cell according to the present invention will be exemplified, and it will be understood that the flexible carbon paper and the method of manufacturing the same, the gas diffusion layer, and the fuel cell according to the present invention are not limited to the following examples.
The following examples and comparative examples each prepared flexible carbon paper using the apparatus shown in fig. 1.
Example 1
(1) Introducing nitrogen into the chemical vapor deposition furnace, removing air in an inner cavity and an outer cavity of the chemical vapor deposition furnace, heating the chemical vapor deposition furnace to 1100 ℃, and preserving heat;
(2) injecting the prepared carbon-containing precursor (the volume ratio of ethanol to chlorobenzene is 1:1) into an inner cavity of a chemical vapor deposition furnace, and controlling the injection rate to be 5.0 mL/min;
(3) placing carbon-based paper with the width of 400mm on a uniform-speed conveyor belt, and conveying the carbon-based paper into an inner cavity of a chemical vapor deposition furnace through the conveyor belt so as to form a carbon film on the surface of the carbon-based paper; the running speed of the conveyor belt is 1.0m/min, and the length of the inner cavity of the chemical vapor deposition furnace is 5 m;
(4) after the carbon film is grown, the carbon paper is conveyed out from the other end of the equipment along with the movement of the conveyor belt, and the flexible carbon paper is obtained.
Example 2
The method is basically the same as the example 1, except that in the step (2), the injection rate of the prepared carbon-containing precursor (the volume ratio of ethanol to chlorobenzene is 1:1) into the inner cavity of the chemical vapor deposition furnace is 2 mL/min.
Example 3
The method is basically the same as example 1, except that the carbon-containing precursors are chloroform and ethanol in a volume ratio of 1: 1.
Example 4
(1) Introducing nitrogen into the chemical vapor deposition furnace, removing air in an inner cavity and an outer cavity of the chemical vapor deposition furnace, heating the chemical vapor deposition furnace to 1100 ℃, and preserving heat;
(2) injecting the prepared carbon-containing precursor (the volume ratio of ethanol to tetrachloromethane is 1:1) into an inner cavity of a chemical vapor deposition furnace, and controlling the injection rate to be 5.0 mL/min;
(3) placing carbon-based paper with the width of 400mm on a uniform-speed conveyor belt, conveying the carbon-based paper into an inner cavity of a chemical vapor deposition furnace through the conveyor belt, and forming a carbon film on the surface of the carbon-based paper; the running speed of the conveyor belt is 0.1m/min, and the length of the inner cavity of the chemical vapor deposition furnace is 5 m;
(4) and after the carbon film grows, the carbon paper is conveyed out from the other end of the equipment along with the movement of the conveyor belt, so that the flexible carbon paper is obtained.
Example 5
The same as in example 1, except that in step (3), the belt was run at a speed of 10 m/min.
Example 6
(1) Introducing nitrogen into the chemical vapor deposition furnace, removing air in an inner cavity and an outer cavity of the chemical vapor deposition furnace, and heating the chemical vapor deposition furnace to 900 ℃ for heat preservation;
(2) injecting the prepared carbon-containing precursor (the volume ratio of ethanol to chlorobenzene is 1:1) into an inner cavity of a chemical vapor deposition furnace, and controlling the injection rate to be 5.0 mL/min;
(3) placing carbon-based paper with the width of 400mm on a uniform-speed conveyor belt, conveying the carbon-based paper into an inner cavity of a chemical vapor deposition furnace through the conveyor belt, and forming a carbon film on the surface of the carbon-based paper; the running speed of the conveyor belt is 0.1m/min, and the length of the inner cavity of the chemical vapor deposition furnace is 10 m;
(4) after the carbon film is grown, the carbon paper is conveyed out from the other end of the equipment along with the movement of the conveyor belt, and the flexible carbon paper is obtained.
Example 7
(1) Introducing nitrogen into the chemical vapor deposition furnace, removing air in an inner cavity and an outer cavity of the chemical vapor deposition furnace, and heating the chemical vapor deposition furnace to 1200 ℃ for heat preservation;
(2) injecting the prepared carbon-containing precursor (the volume ratio of ethanol to chlorobenzene is 1:1) into an inner cavity of a chemical vapor deposition furnace, and controlling the injection rate to be 5.0 mL/min;
(3) placing carbon-based paper with the width of 400mm on a uniform-speed conveyor belt, conveying the carbon-based paper into an inner cavity of a chemical vapor deposition furnace through the conveyor belt, and forming a carbon film on the surface of the carbon-based paper; the running speed of the conveyor belt is 2m/min, and the length of the inner cavity of the chemical vapor deposition furnace is 20 m;
(4) after the carbon film is grown, the carbon paper is conveyed out from the other end of the equipment along with the movement of the conveyor belt, and the flexible carbon paper is obtained.
Example 8
(1) Introducing nitrogen into the chemical vapor deposition furnace, removing air in an inner cavity and an outer cavity of the chemical vapor deposition furnace, and heating the chemical vapor deposition furnace to 1200 ℃ for heat preservation;
(2) injecting the prepared carbon-containing precursor (the volume ratio of ethanol to o-dichlorobenzene is 1:1) into an inner cavity of the chemical vapor deposition furnace, and controlling the injection rate to be 10 mL/min;
(3) placing carbon-based paper with the width of 400mm on a uniform-speed conveyor belt, conveying the carbon-based paper into an inner cavity of a chemical vapor deposition furnace through the conveyor belt, and forming a carbon film on the surface of the carbon-based paper; the running speed of the conveyor belt is 1.0m/min, and the length of the inner cavity of the chemical vapor deposition furnace is 5 m;
(4) after the carbon film is grown, the carbon paper is conveyed out from the other end of the equipment along with the movement of the conveyor belt, and the flexible carbon paper is obtained.
Example 9
The same as example 1, except that in the step (2), the volume ratio of ethanol to chlorobenzene in the carbon-containing precursor was 1: 0.5.
Example 10
The same as example 1, except that in the step (2), the volume ratio of ethanol to chlorobenzene in the carbon-containing precursor was 1: 3.
Example 11
The process was substantially the same as in example 1, except that in step (2), the carbon-containing precursor contained chlorobenzene only and no ethanol.
Comparative example 1
The process was substantially the same as in example 1, except that the carbon-containing precursors were toluene and ethanol at a volume ratio of 1: 1.
Comparative example 2
The same as example 1, except that the carbon-containing precursor was ethanol.
Comparative example 3
The same as example 1, except that the carbon-containing precursor was xylene and ethanol at a volume ratio of 1: 1.
The condition parameters of each example and comparative example are shown in table 1.
TABLE 1
Performance testing
Flexibility: the flexibility of the carbon paper is evaluated by a method of measuring the bending displacement of the middle position by the fixing force, and the larger the bending displacement is, the better the flexibility is. The flexible carbon paper prepared in each of examples and comparative examples was cut into a size of 10mm × 110mm, centered on a parallel-supported frame spaced 80mm apart, and a force (50mN or 100mN) was applied to the middle of the flexible carbon paper to record the bending displacement of the middle of the flexible carbon paper, thereby ensuring that the carbon paper was not crushed during the test, and the test results are shown in table 2.
Porosity: the porosity of the flexible carbon papers prepared in each of the examples and comparative examples was measured using a U.S. Gurley4110N air permeability tester, and the results are shown in table 2.
Conductivity: the resistivity of the flexible carbon paper prepared in each example and comparative example was measured using a Ningbor FT-541SJB-341 automatic resistance tester, and the test results are shown in Table 2.
TABLE 2
As can be seen from the table 2, compared with the comparative ratio of 1-3, the flexibility of the flexible carbon paper prepared in the embodiment is effectively improved, and the flexible carbon paper has a large porosity; further, embodiment 1 ~ 8 have still promoted the electric conductivity of carbon paper simultaneously.
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, which is convenient for specific and detailed understanding of the technical solutions of the present invention, but the present invention should not be construed as being limited to the 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 (11)
1. The flexible carbon paper is characterized by comprising carbon-based paper and a carbon film, wherein the carbon film is deposited on the surface of the carbon-based paper by adopting a chemical vapor deposition method, and a carbon-containing precursor used in the chemical vapor deposition method contains chlorinated organic matters.
2. A flexible carbon paper as claimed in claim 1 wherein said chlorinated organic compound is at least one of chlorinated aromatic compound and chlorinated C1-C4 alkane.
3. A flexible carbon paper as claimed in claim 2 wherein the chlorinated organic is selected from at least one of chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, dichloromethane, trichloromethane, tetrachloromethane and 1, 2-dichloroethane.
4. A flexible carbon paper according to any one of claims 1 to 3 wherein the carbon-containing precursor further comprises a non-chlorinated organic.
5. A flexible carbon paper as claimed in claim 4 wherein said non-chlorinated organic is selected from at least one of ethanol, ethyl acetate and toluene.
6. A flexible carbon paper as claimed in claim 4 wherein the volume ratio of chlorinated organics to non-chlorinated organics in the chemical vapour deposition is 1 (0.1: 10).
7. A method of making a flexible carbon paper as claimed in any one of claims 1 to 6, comprising the steps of:
and depositing a carbon film on the surface of the carbon-based paper by adopting a chemical vapor deposition method.
8. The method according to claim 7, wherein the reaction temperature in the chemical vapor deposition is 900 to 1200 ℃ and the reaction time is 0.5 to 120 min.
9. The method of claim 7, wherein the chemical vapor deposition comprises the steps of:
and introducing the carbon-based paper into a furnace chamber of a chemical vapor deposition furnace by adopting a conveyor belt for chemical vapor deposition, wherein the furnace chamber comprises an outer cavity and an inner cavity arranged in the outer cavity, nitrogen or argon is filled into the outer cavity, and the carbon-containing precursor is filled into the inner cavity for deposition.
10. A gas diffusion layer comprising the flexible carbon paper of any of claims 1 to 6.
11. A fuel cell, characterized in that the electrode of the fuel cell comprises a gas diffusion layer according to claim 10.
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