CN114195129A - Carbon nano elastomer material and preparation method thereof, gas diffusion membrane and battery - Google Patents
Carbon nano elastomer material and preparation method thereof, gas diffusion membrane and battery Download PDFInfo
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- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims description 7
- 238000003776 cleavage reaction Methods 0.000 claims description 7
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- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 2
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 14
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- SNHMUERNLJLMHN-IDEBNGHGSA-N iodobenzene Chemical group I[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 SNHMUERNLJLMHN-IDEBNGHGSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/26—Mechanical properties
Abstract
The invention discloses a carbon nano elastomer material and a preparation method thereof, a gas diffusion membrane and a battery. In the preparation method of the carbon nano elastomer material, under the action of reducing gas and a reduction reaction catalyst, a carbon source is subjected to cracking reaction on a limited-area template to deposit carbon, so that the carbon nano elastomer material is prepared; wherein the carbon source is selected from benzene substituted by halogen, and the halogen is selected from at least one of chlorine and bromine. The preparation method can prepare the carbon nano elastomer material with the three-dimensional cross-linked network structure, and has high conductivity and high porosity. When the carbon nano elastomer material is used for preparing the gas diffusion membrane, the carbon nano elastomer material can be used as a supporting layer material to play a role of elastic support, and meanwhile, the conductivity and the porosity of the gas diffusion membrane can be improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a carbon nano elastomer material, a preparation method thereof, a gas diffusion membrane and a battery.
Background
The fuel cell is a novel energy conversion device, can convert chemical energy into electric energy without pollution, has the advantages of high power density, low working temperature, quick start, long service life and the like, and is widely concerned by researchers. The core component of the fuel cell is a membrane electrode with a sandwich structure, and a proton exchange membrane, a cathode catalyst layer, an anode catalyst layer and a cathode gas diffusion layer and an anode gas diffusion layer which are arranged outside the catalyst layers are sequentially arranged from the center to two sides.
Gas diffusion layers play an important role in fuel cells, and their roles are mainly: (1) the catalyst layer is supported to prevent the catalyst from falling off; (2) a transportation channel is provided for gas and water, so that the reaction gas can uniformly and stably reach a reaction area, and the product water can be smoothly discharged to avoid blocking the gas channel; (3) as an electrode material, the material plays a role of an electron channel; (4) the heat generated from the battery is radiated to the outside. The Gas Diffusion Layer (GDL) is mainly composed of a microporous layer and a support layer, and the support layer is required to have good electron conductivity, excellent gas permeability, and to play a supporting role. The traditional support layer is generally made of porous conductive materials, carbon paper is a support layer material of the most widely applied GDL, carbon fibers are mainly used as a framework, but the carbon fibers are smooth in surface, low in surface energy and few in polar functional groups, so that hydrogen bonds are difficult to form among the carbon fibers, and the carbon fibers are difficult to disperse. Therefore, the preparation of the gas diffusion layer by using the carbon fiber paper as the supporting layer has high technical barrier, complex and tedious process, difficult popularization of mass production and low porosity of the prepared gas diffusion layer.
Thus, the prior art remains to be improved.
Disclosure of Invention
Based on the carbon nano elastomer material, the preparation method thereof, the gas diffusion membrane and the battery are provided, and the carbon nano elastomer material prepared by the preparation method of the carbon nano elastomer material has a three-dimensional cross-linked network structure and is high in compressibility, conductivity and porosity.
The technical scheme of the invention is as follows.
In one aspect of the present invention, a method for preparing a carbon nanoelastomer material is provided, which comprises the following steps:
under the action of reducing gas and a reduction reaction catalyst, a carbon source is subjected to cracking reaction on a limited-area template to deposit carbon, so that the carbon nano elastomer material is prepared;
wherein the carbon source is selected from benzene substituted by halogen, and the halogen is selected from at least one of chlorine and bromine.
In some of these embodiments, the cleavage reaction is performed under the influence of a plasma.
In some of these embodiments, the carbon source is selected from at least one of bromobenzene, 1, 2-dibromobenzene, 1, 3-dibromobenzene, p-dibromobenzene, chlorobenzene, 1, 2-dichlorobenzene, p-dichlorobenzene, and 1, 3-dichlorobenzene.
In some embodiments, the temperature of the cracking reaction is 750-1000 ℃ and the time is 0.5-600 min.
In some of these embodiments, the following steps are included:
mixing the carbon source and the reduction reaction catalyst to prepare a mixture;
and filling the mixture of the reducing gas and the vaporized gas into the reactor with the confinement template, and carrying out the cracking reaction and carbon deposition.
In some of these embodiments, the cleavage reaction is conducted under a protective gas; the volume ratio of the reducing gas to the protective gas is (0.1-0.5): 1. In some of these embodiments, the confinement template has a thickness in the range of 1 μm to 1000 μm.
In another aspect of the present invention, there is provided a carbon nanoelastomer material, which is prepared by the above-mentioned method for preparing a carbon nanoelastomer material.
In yet another aspect of the present invention, there is provided a gas diffusion membrane comprising a microporous layer and a support layer, the support layer being a raw material comprising a carbon nanoelastomer material as described above.
In yet another aspect of the present invention, there is provided a battery comprising a gas diffusion membrane as described above.
In the preparation method of the carbon nano elastomer material, under the action of reducing gas and a reduction reaction catalyst, a carbon source is subjected to cracking reaction on a limited-area template to deposit carbon, the limited-area template has a macroscopic limited-area plane space, under the action of a macroscopic limited-area effect of the macroscopic limited-area plane space, the carbon source is subjected to cracking reaction on the limited-area template and carbon deposition to form carbon nano tubes with a porous network structure, and the formed carbon nano tubes are mutually crosslinked by adopting a specific type of carbon source to prepare the carbon nano elastomer material with the three-dimensional crosslinked network structure. And the preparation method has simple process and is suitable for large-scale production.
Further, in the preparation method of the carbon nano elastomer material, the steps of carrying out cracking reaction on a carbon source on the limited-area template and carbon deposition are carried out under the action of plasma, and the plasma can promote mutual crosslinking among the carbon nano tubes and improve the crosslinking strength of the prepared carbon nano tubes.
Drawings
FIG. 1 is a scanning electron micrograph of the carbon nanoelastomer material prepared in example 1;
FIG. 2 is a schematic diagram of the cleavage reaction carried out in example 1.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, 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.
Carbon nanotubes have excellent electrical conductivity, and technicians have attempted to prepare a gas diffusion layer using carbon nanotubes to improve the electrical conductivity of the gas diffusion layer. However, the conventional method for preparing the carbon nanotube material is limited to the formation of a micro-porous nanotube structure, and cannot form a self-supporting structure having a three-dimensional network structure. Therefore, in the conventional technology, only carbon nanotubes can be directly grown on carbon paper as a conductive microporous layer to improve the conductivity of the gas diffusion layer, the carbon paper is still the most widely used support layer material of GDL, but the carbon paper as the support layer for preparing the gas diffusion layer has high technical barrier and complex and tedious process, and is difficult to popularize large-scale production.
In order to solve the problem, the technicians of the invention make creative and large-scale researches and provide the following carbon nano elastomer material, a preparation method thereof, a gas diffusion membrane and a battery.
One embodiment of the present invention provides a method for preparing a carbon nanoelastomer material, including the following step S1.
And step S1, under the action of reducing gas and a reduction reaction catalyst, carrying out cracking reaction on a carbon source on the limited-area template to deposit carbon, thus obtaining the carbon nano elastomer material.
Wherein the carbon source is selected from benzene substituted by halogen, and the halogen is selected from at least one of chlorine and bromine.
In the preparation method of the carbon nano elastomer material, under the action of reducing gas and a reduction reaction catalyst, a carbon source is subjected to cracking reaction on a limited-area template to deposit carbon, the limited-area template has a macroscopic limited-area plane space, under the action of a macroscopic limited-area effect of the macroscopic limited-area plane space, the carbon source is subjected to cracking reaction on the limited-area template and carbon deposition is carried out to form the carbon nano tubes with the porous network structure, and the formed carbon nano tubes are mutually crosslinked by adopting a specific type of carbon source to prepare the carbon nano elastomer material with the three-dimensional crosslinked network structure, so that the carbon nano elastomer material has high conductivity and high porosity.
When the carbon nano elastomer material is used for preparing the gas diffusion membrane, the carbon nano elastomer material can be used as a supporting layer material to play a role of elastic support, and meanwhile, the conductivity and the porosity of the gas diffusion membrane can be improved.
In some embodiments, the cracking reaction is performed by plasma in step S1.
In the preparation method of the carbon nano elastomer material, the carbon source is subjected to cracking reaction on the limited-area template under the action of the plasma, and the plasma can promote the mutual crosslinking among the carbon nano tubes and improve the crosslinking strength of the prepared carbon nano tubes.
Specifically, the plasma is emitted by a plasma emitter.
In some of these embodiments, the benzene substituted with halogen may be benzene mono-or poly-substituted with halogen.
In some of these embodiments, the halogen is selected from bromine. Specifically, the compound comprises at least one of bromobenzene, 1, 2-dibromobenzene, 1, 3-dibromobenzene and p-dibromobenzene.
In some of these embodiments, the halogen is selected from chlorine. Specifically, it includes at least one of chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene and p-dichlorobenzene.
Further, the carbon source is at least one selected from the group consisting of bromobenzene, 1, 2-dibromobenzene, 1, 3-dibromobenzene, p-dibromobenzene, chlorobenzene, 1, 2-dichlorobenzene, p-dichlorobenzene and 1, 3-dichlorobenzene.
In some embodiments, the temperature of the cracking reaction is 750-1000 ℃ and the time is 0.5-600 min.
At a suitable temperature, the cracking reaction can be further promoted.
The above-mentioned reduction reaction catalyst may be a catalyst commonly used in the art that can catalyze a reduction pyrolysis reaction.
In some embodiments, the reduction catalyst is a metal catalyst, and further, the reduction catalyst is an iron catalyst.
In some of these embodiments, the reduction catalyst is ferrocene.
In some of these embodiments, the reducing atmosphere is formed by introducing a reducing gas.
Specifically, the reducing gas is hydrogen.
In some of these embodiments, the cleavage reaction described above is carried out under a protective gas; further, a protective gas is introduced simultaneously with the reducing gas.
In some of these embodiments, the protective gas comprises at least one of nitrogen, argon, and helium.
Further, the volume ratio of the reducing gas to the protective gas is (0.1 to 0.5): 1.
In some embodiments, the step of cracking reaction and carbon deposition in step S1 includes the following steps S10-S20.
And step S10, mixing the carbon source and the reduction reaction catalyst to prepare a mixture.
And step S20, filling the reducing gas and the vaporized mixture into a reactor with a confinement template, and performing cracking reaction and carbon deposition.
In some embodiments, the mass ratio of the carbon source to the reduction catalyst is (0.005-0.1): 1.
Further, in step S20, before the step of charging the reducing gas and the vaporized mixture into the reactor with the confinement template, the method further comprises the following steps:
protective gas is filled into a reactor with a limited-area template to remove air, and then the temperature is raised to 500 ℃ at the temperature rise speed of 1-10 ℃/min.
Further, in step S20, the reducing gas is charged first, and the vaporized mixture is charged while maintaining the charging of the protective gas.
Further, the temperature of the step of the cracking reaction and the carbon deposition is 750-1000 ℃, and then in step S20, when the reducing gas is filled into the reactor with the limited-area template, the temperature is continuously increased to 750-1000 ℃ at the temperature increasing speed of 1-10 ℃/min, and then the vaporized mixture is filled.
It is understood that when the above-mentioned steps of the cleavage reaction and the carbon deposition are also performed by the plasma, the plasma emitter is turned on to emit the plasma into the reactor having the confinement template while the vaporized mixture is charged in step S20.
In some embodiments, step S20 further includes removing the confinement template after the step of cracking reaction and carbon deposition.
In some of these embodiments, the confinement template has a thickness in the range of 1 μm to 1000 μm.
The domain-limited template is a template with a domain-limited effect, and the material of the domain-limited template includes but is not limited to: stainless steel, titanium plate, ceramic plate, quartz plate and other high temperature resistant plates.
One embodiment of the present invention provides a carbon nanoelastomer material, which is prepared by the above-mentioned method for preparing a carbon nanoelastomer material.
The carbon nano elastomer material prepared by the preparation method of the carbon nano elastomer material has a three-dimensional cross-linked network structure, and has compressible elasticity, high conductivity and high porosity. When the carbon nano elastomer material is used for preparing the gas diffusion membrane, the carbon nano elastomer material can be used as a supporting layer material to play a role of elastic support, and meanwhile, the conductivity and the porosity of the gas diffusion membrane can be improved.
An embodiment of the present invention also provides a gas diffusion membrane including a microporous layer and a support layer made of a material containing the carbon nanoelastomer material described above.
The carbon nano elastomer material has a three-dimensional cross-linked network structure, has compressible elasticity, can play a supporting role, and is high in conductivity and porosity.
The microporous layer can be made of a microporous layer material commonly used in the art.
In some embodiments, the microporous layer is prepared from a material comprising carbon and polytetrafluoroethylene.
An embodiment of the present invention provides a battery comprising a gas diffusion membrane as described above.
The battery includes the gas diffusion film as described above, and is excellent in electrical conductivity.
In some embodiments, the battery is a fuel cell, and further, the battery includes: the proton exchange membrane comprises a proton exchange membrane, a cathode catalyst layer, a cathode gas diffusion layer, an anode catalyst layer and an anode gas diffusion layer; the cathode catalyst layer and the anode catalyst layer are respectively arranged on two sides of the proton exchange membrane, the cathode gas diffusion layer is arranged on one side, far away from the proton exchange membrane, of the cathode catalyst layer, and the anode gas diffusion layer is arranged on one side, far away from the proton exchange membrane, of the anode catalyst layer.
The cathode gas diffusion layer and/or the anode gas diffusion layer employ a gas diffusion membrane as described above.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
The method comprises the following specific steps:
(1) and mixing bromobenzene as a carbon source and ferrocene as a catalyst to obtain a mixture. Wherein the mass ratio of bromobenzene to ferrocene is 0.03: 1.
(2) Specifically, referring to FIG. 2 (a), argon Ar is introduced into a confined planar reactor, after air is removed, argon is continuously introduced, the temperature is raised at a rate of 5 ℃/min, and when the temperature is raised to 500 ℃, hydrogen H is introduced2The volume ratio of hydrogen to argon in the reactor was made 0.2 by adjusting the flow rates of hydrogen and argon. Wherein, the thickness of the confinement template 10 of the confinement planar reactor is 100 μm, and the material is a metallic titanium plate. When the temperature is raised to 880 ℃, the vaporized mixture is introduced, and the plasma emitter is turned on to emit plasma into the confinement planar reactor, so that the carbon source is subjected to a cracking reaction on the confinement template 10 and carbon deposition for 30min under the action of the catalyst, and the carbon nano-elastomer material with a porous network structure is formed on the confinement template 10, as shown in (b) of fig. 2. Wherein the power of the plasma emitter is 2 kW.
(3) And after the reaction is finished, stopping introducing the mixture, stopping introducing argon and hydrogen when the temperature is reduced to room temperature, taking out the limited-area planar reaction equipment, and removing the limited-area template to obtain the carbon nano elastomer material with the porous network structure, wherein an electron microscope image of the carbon nano elastomer material is shown in fig. 1.
Example 2
(1) And mixing bromobenzene as a carbon source and ferrocene as a catalyst to obtain a mixture. Wherein the mass ratio of bromobenzene to ferrocene is 0.1: 1.
(2) And introducing argon Ar into the confined planar reactor, continuously introducing argon after air is completely removed, heating at the heating speed of 10 ℃/min, introducing hydrogen when the temperature is increased to 500 ℃, and adjusting the flow of the hydrogen and the argon to ensure that the volume ratio of the hydrogen to the argon is 0.5. Wherein the thickness of the confinement template of the confinement planar reactor is 300 μm. When the temperature is increased to 900 ℃, the vaporized mixture is introduced, and simultaneously a plasma emitter is turned on to emit plasma into the confinement plane reactor, so that the cracking reaction is carried out and carbon deposition is carried out for 60 min. Wherein, the power of the plasma emitter is 200W, and the material of the confinement template is the same as that of the confinement template used in the step (2) in the embodiment 1.
(3) And after the reaction is finished, stopping introducing the mixture, stopping introducing argon and hydrogen when the temperature is reduced to room temperature, taking out the limited area planar reaction equipment, and removing the limited area template to obtain the carbon nano elastomer material with the porous network structure.
Example 3
(1) The carbon source is 1, 2-dibromobenzene, the catalyst is ferrocene, and the 1, 2-dibromobenzene and the ferrocene are mixed to obtain a mixture. Wherein the mass ratio of the 1, 2-dibromobenzene to the ferrocene is 0.2: 1.
(2) And introducing argon into the confined planar reactor, continuously introducing argon after air is completely removed, heating at the heating speed of 10 ℃/min, starting introducing hydrogen when the temperature is increased to 500 ℃, and adjusting the flow of the hydrogen and the argon to ensure that the volume ratio of the hydrogen to the argon is 0.5. Wherein the thickness of the confinement template of the confinement planar reactor is 1000 μm. When the temperature rises to 1000 ℃, the vaporized mixture is introduced, and simultaneously a plasma emitter is turned on to emit plasma into the confinement plane reactor, so that the cracking reaction is carried out and carbon deposition is carried out for 60 min. Wherein, the power of the plasma emitter is 5kW, and the material of the confinement template is the same as that of the confinement template used in the step (2) of the embodiment 1.
(3) And after the reaction is finished, stopping introducing the mixture, stopping introducing argon and hydrogen when the temperature is reduced to room temperature, taking out the limited area planar reaction equipment, and removing the limited area template to obtain the carbon nano elastomer material with the porous network structure.
Example 4
(1) The carbon source is 1, 3-dibromobenzene, the catalyst is ferrocene, and the 1, 3-dibromobenzene and the ferrocene are mixed to obtain a mixture. Wherein the mass ratio of the 1, 3-dibromobenzene to the ferrocene is 0.05: 1.
(2) And introducing argon into the confined planar reactor, continuously introducing argon after air is completely removed, heating at the heating speed of 10 ℃/min, introducing hydrogen when the temperature is increased to 500 ℃, and adjusting the flow of the hydrogen and the argon to ensure that the volume ratio of the hydrogen to the argon is 0.2. Wherein the thickness of the confinement template of the confinement planar reactor is 50 μm. When the temperature rises to 800 ℃, the vaporized mixture is introduced, and simultaneously a plasma emitter is turned on to emit plasma into the confinement plane reactor, so that the cracking reaction is carried out and carbon deposition is carried out for 2 min. Wherein, the power of the plasma emitter is 10kW, and the material of the confinement template is the same as that of the confinement template used in the step (2) of the embodiment 1.
(3) And after the reaction is finished, stopping introducing the mixture, stopping introducing argon and hydrogen when the temperature is reduced to room temperature, taking out the limited area planar reaction equipment, and removing the limited area template to obtain the carbon nano elastomer material with the porous network structure.
Example 5
(1) The carbon source is chlorobenzene, the catalyst is ferrocene, and the bromobenzene and the ferrocene are mixed to obtain a mixture. Wherein the mass ratio of chlorobenzene to ferrocene is 0.06: 1.
(2) And introducing argon into the confined planar reactor, continuously introducing argon after air is completely removed, heating at the heating speed of 10 ℃/min, introducing hydrogen when the temperature is increased to 500 ℃, and adjusting the flow of the hydrogen and the argon to ensure that the volume ratio of the hydrogen to the argon is 0.5. Wherein the thickness of the confinement template of the confinement planar reactor is 300 μm. When the temperature is increased to 900 ℃, the vaporized mixture is introduced, and simultaneously a plasma emitter is turned on to emit plasma into the confinement plane reactor, so that the cracking reaction is carried out and carbon deposition is carried out for 60 min. Wherein, the power of the plasma emitter is 200W, and the material of the confinement template is the same as that of the confinement template used in the step (2) in the embodiment 1.
(3) And after the reaction is finished, stopping introducing the mixture, stopping introducing argon and hydrogen when the temperature is reduced to room temperature, taking out the limited area planar reaction equipment, and removing the limited area template to obtain the carbon nano elastomer material with the porous network structure.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: the carbon source in step (1) of example 1 was replaced with an equal mass of ethane.
Other steps and conditions were the same as in example 1.
Comparative example 2
(1) Comparative example 2 is substantially the same as example 1 except that: the carbon source in step (1) of example 1 was replaced with benzene of equal mass.
Other steps and conditions were the same as in example 1.
Comparative example 3
(1) Comparative example 3 is substantially the same as example 1 except that: the carbon source in step (1) of example 1 was replaced with toluene of equal mass.
Other steps and conditions were the same as in example 1.
Comparative example 4
(1) Comparative example 4 is substantially the same as example 1 except that: the carbon source in step (1) of example 1 was replaced with iodobenzene of equal mass.
Other steps and conditions were the same as in example 1.
Comparative example 5
(1) Same as in step (1) of example 1.
(2) And introducing argon into the closed reactor, continuously introducing argon after air is completely removed, heating at the heating speed of 5 ℃/min, and introducing hydrogen when the temperature is increased to 500 ℃, wherein the volume ratio of the hydrogen to the argon is 0.2. Wherein, the height of the sealed space is 100 cm. When the temperature rises to 880 ℃, the vaporized mixture is introduced, and simultaneously a plasma emitter is turned on to emit plasma into the confinement plane reactor, so that the cracking reaction is carried out and carbon deposition is carried out for 30 min. Wherein the power of the plasma emitter is 2kW
(3) And after the reaction is finished, stopping introducing the mixture, stopping introducing argon and hydrogen when the temperature is reduced to room temperature, taking out the limited area planar reaction equipment, and removing the limited area template to obtain the carbon nano material with the porous structure.
The prepared carbon nanomaterial with the porous structure has irregular surface, uneven surface and too large thickness, and is not suitable for a gas diffusion layer of a fuel cell.
Performance testing
The performance of the materials prepared in examples 1-5 and comparative examples 1-5 was tested as follows:
(1) the conductivity in the thickness direction of the materials prepared in examples 1 to 5 and comparative examples 1 to 5 was tested, and the test process was as follows with reference to part 7 of a proton exchange membrane fuel cell in standard GB/T20042.7-2014: the specific test results of the carbon paper property test method are shown in table 1.
TABLE 1
| Conductivity (m omega cm) | |
| Example 1 | 5.6 |
| Example 2 | 4.9 |
| Example 3 | 4.5 |
| Example 4 | 7.8 |
| Example 5 | 6.8 |
| Comparative example 1 | Powder form, not measurable |
| Comparative example 2 | Powder form, not measurable |
| Comparative example 3 | Powder form, not measurable |
| Comparative example 4 | Powder form, not measurable |
| Comparative example 5 | 41.3 |
(2) The porosity of the carbon nano elastomer materials prepared in the examples 1 to 5 and the comparative examples 1 to 5 is tested, and the test process refers to the 7 th part of a proton exchange membrane fuel cell in the standard GB/T20042.7-2014: the specific test results of the carbon paper property test method are shown in Table 2.
TABLE 2
| Porosity of the material | |
| Example 1 | 83.2％ |
| Example 2 | 78.1％ |
| Example 3 | 75.4％ |
| Example 4 | 86.3％ |
| Example 5 | 84.6％ |
| Comparative example 1 | 96.3％ |
| Comparative example 2 | 94.1％ |
| Comparative example 3 | 92.1％ |
| Comparative example 4 | 95.8％ |
| Comparative example 5 | 76.9％ |
(3) The densities of the carbon nano elastomer materials prepared in the examples 1 to 5 and the comparative examples 1 to 5 are tested, and the test process refers to the 7 th part in the standard GB/T20042.7-2014 proton exchange membrane fuel cell: the specific test results of the carbon paper property test method are shown in Table 3.
TABLE 3
| Density of | |
| Example 1 | 48.6mg/cm3 |
| Example 2 | 42.6mg/cm3 |
| Example 3 | 65.6mg/cm3 |
| Example 4 | 25.6mg/cm3 |
| Example 5 | 31.4mg/cm3 |
| Comparative example 1 | 25.6mg/cm3 |
| Comparative example 2 | 25.6mg/cm3 |
| Comparative example 3 | 25.6mg/cm3 |
| Comparative example 4 | 25.6mg/cm3 |
| Comparative example 5 | 25.6mg/cm3 |
(4) The compression strength of the carbon nano elastomer materials prepared in the examples 1-5 and the comparative examples 1-5 is tested, the test process refers to the standard GBT 34559-.
TABLE 4
| Compressive strength | |
| Example 1 | 16.3Mpa |
| Example 2 | 24.5Mpa |
| Example 3 | 27.3Mpa |
| Example 4 | 19.4Mpa |
| Example 5 | 20.3Mpa |
| Comparative example 1 | 0.3Mpa |
| Comparative example 2 | 0.4Mpa |
| Comparative example 3 | 0.3Mpa |
| Comparative example 4 | 0.2Mpa |
| Comparative example 5 | 7.3Mpa |
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, and the description thereof is more specific and detailed, but not construed as limiting 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. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a carbon nano elastomer material is characterized by comprising the following steps:
under the action of reducing gas and a reduction reaction catalyst, a carbon source is subjected to cracking reaction on a limited-area template to deposit carbon, so that the carbon nano elastomer material is prepared;
wherein the carbon source is selected from benzene substituted by halogen, and the halogen is selected from at least one of chlorine and bromine.
2. The method for preparing a carbon nanoelastomer material according to claim 1, wherein the cleavage reaction is performed under the action of plasma.
3. The method for producing a carbon nanoelastomeric material according to claim 1, wherein the carbon source is selected from at least one of bromobenzene, 1, 2-dibromobenzene, 1, 3-dibromobenzene, p-dibromobenzene, chlorobenzene, 1, 2-dichlorobenzene, p-dichlorobenzene, and 1, 3-dichlorobenzene.
4. The method for preparing a carbon nanoelastomer material according to any one of claims 1 to 3, wherein the temperature of the pyrolysis reaction is 750 ℃ to 1000 ℃ and the time is 0.5min to 600 min.
5. The method for producing a carbon nanoelastomer material according to any one of claims 1 to 3, comprising the steps of:
mixing the carbon source and the reduction reaction catalyst to prepare a mixture;
and filling the mixture of the reducing gas and the vaporized reducing gas into a reactor with the confinement template, and carrying out the cracking reaction and carbon deposition.
6. The method for preparing a carbon nanoelastomer material according to claim 5, wherein the cleavage reaction is performed under a protective gas; the volume ratio of the reducing gas to the protective gas is (0.1-0.5): 1.
7. The method for producing a carbon nanoelastomer material according to any one of claims 1 to 3, wherein the thickness of the domain-limiting template is 1 μm to 1000 μm.
8. A carbon nanoelastomer material prepared by the method for preparing a carbon nanoelastomer material according to any one of claims 1 to 7.
9. A gas diffusion membrane comprising a microporous layer and a support layer, wherein the support layer comprises the carbon nanoelastomer material of claim 8.
10. A battery comprising the gas diffusion membrane of claim 9.
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