CN117239170A - Proton exchange membrane hydrogen fuel cell C/C composite bipolar plate and preparation and application thereof - Google Patents

Proton exchange membrane hydrogen fuel cell C/C composite bipolar plate and preparation and application thereof Download PDF

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Publication number
CN117239170A
CN117239170A CN202311183178.XA CN202311183178A CN117239170A CN 117239170 A CN117239170 A CN 117239170A CN 202311183178 A CN202311183178 A CN 202311183178A CN 117239170 A CN117239170 A CN 117239170A
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bipolar plate
composite material
fuel cell
hydrogen fuel
exchange membrane
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王梦千
董凯
邓建基
汤哲鹏
程仁政
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EIGHTH RESEARCH INSTITUTE OF NUCLEAR TECHNOLOGY
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EIGHTH RESEARCH INSTITUTE OF NUCLEAR TECHNOLOGY
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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Abstract

The invention relates to the technical field of bipolar plates of proton exchange membrane hydrogen fuel cells, in particular to a C/C composite bipolar plate of a proton exchange membrane hydrogen fuel cell and preparation and application thereof. The invention firstly carries out compression molding, solidification and forming on a carbon fiber preform and high-carbon resin slurry, then carries out carbonization treatment once, carries out impregnation densification and high-temperature graphitization treatment on the high-carbon resin slurry, and processes the high-carbon resin slurry to obtain a C/C composite material bipolar plate semi-finished product; and finally, carrying out hole sealing on the surface coating of the pyrolytic carbon by chemical vapor deposition, and carrying out post-treatment to obtain the bipolar plate of the C/C composite material of the proton exchange membrane hydrogen fuel cell. The carbon fiber in the C/C composite bipolar plate has good conductivity and high chemical stability, and can be used as a skeleton reinforcement to improve the bending strength of the C/C composite bipolar plate; the conductivity of the C/C composite bipolar plate can be obviously improved by means of asphalt impregnation densification and high-temperature heat treatment; the densified C/C composite bipolar plate is easy to process and light in weight.

Description

Proton exchange membrane hydrogen fuel cell C/C composite bipolar plate and preparation and application thereof
Technical Field
The invention relates to the technical field of bipolar plates of proton exchange membrane hydrogen fuel cells, in particular to a C/C composite bipolar plate of a proton exchange membrane hydrogen fuel cell and preparation and application thereof.
Background
The production cost and the use cost of the hydrogen fuel cell are important factors that hinder the development of the hydrogen fuel cell in the field of new energy automobiles. The proton exchange membrane hydrogen fuel cell is a hydrogen fuel cell which is widely applied at present, and mainly comprises a proton exchange membrane, a bipolar plate, a gas diffusion layer and a catalyst. In recent years, proton exchange membrane hydrogen fuel cell technology research has focused on proton exchange membranes, bipolar plates, control technologies, and the like. The bipolar plate is used as one of the core components of the proton exchange membrane, and accounts for 65% -80% of the total weight, and accounts for 30% -45% of the total cost, so that the development of a novel bipolar plate material with excellent comprehensive performance and high cost performance is beneficial to improving the application space of the hydrogen fuel cell in the field of new energy automobiles, and the thinning and weight reduction of the bipolar plate are key technologies for realizing the light weight of the new energy automobiles in the future. The bipolar plate plays roles in separating fuel and oxidant, collecting conduction current, distributing gas to an electrode reaction layer to generate electrode reaction, effectively radiating heat to ensure uniformity of a battery thermal field, forming a galvanic pile framework by alternately stacking with a membrane electrode and the like in the fuel cell, so that the bipolar plate needs to meet the performance requirements of easiness in processing, low thermal expansion coefficient, high heat conduction and electric conduction, corrosion resistance, excellent mechanical property, good air tightness and long service life.
Currently, the bipolar plate material types for hydrogen fuel cells include: graphite bipolar plates, metal bipolar plates and composite bipolar plates. The metal material has poor corrosion resistance, so that the problems of short service life, unstable performance and the like are caused; the surface modification methods such as plasma spraying, high-temperature coating and the like increase the production cost of the coating. The graphite bipolar plate has limited service life due to high processing difficulty and low mechanical strength, and has high comprehensive cost and is difficult to produce and apply on a large scale. The graphite/carbon fiber/carbon black reinforced resin matrix composite material is taken as the main development direction of the composite material bipolar plate, and has the advantages of both graphite and metal bipolar plates; however, higher graphite/carbon fiber/carbon black contents are required to improve the conductivity of the bipolar plate, which results in reduced gas tightness and mechanical strength; while a higher resin content causes a decrease in the conductivity of the bipolar plate. The three types of bipolar plates, namely the graphite bipolar plate, the metal bipolar plate and the composite bipolar plate, all show certain performance defects in the application of the hydrogen fuel cell and become key factors for restricting the development of the hydrogen fuel cell.
Disclosure of Invention
In order to solve the performance defect and the use defect of the existing bipolar plate material, the invention provides a bipolar plate of a C/C (carbon fiber reinforced carbon matrix) composite material (also simply called as a C/C composite material bipolar plate) of a proton exchange membrane hydrogen fuel cell, and preparation and application thereof. The C/C composite bipolar plate has remarkable performance advantages, wherein the carbon fiber has good conductivity and high chemical stability, can meet the corrosion resistance performance requirement of the bipolar plate material, and can also improve the bending strength of the C/C composite bipolar plate by taking the carbon fiber as a skeleton reinforcement; the conductivity of the C/C composite bipolar plate can be obviously improved by means of asphalt impregnation densification and high-temperature heat treatment; the densified C/C composite bipolar plate is easy to process and light in weight, and can be thinned and weight-reduced.
The aim of the invention can be achieved by the following technical scheme:
the first object of the invention is to provide a preparation method of a bipolar plate of a C/C composite material of a proton exchange membrane hydrogen fuel cell, which comprises the following steps:
(S1) carrying out compression molding, solidification and forming on a carbon fiber preform and high-carbon-residue resin slurry to obtain a resin-based composite material plate;
(S2) carbonizing the resin-based composite material plate prepared in the step (S1) to obtain a low-density C/C composite material plate;
(S3) carrying out impregnation densification on the low-density C/C composite material plate prepared in the step (S2) through high-carbon residue slurry to obtain a high-density C/C composite material plate;
(S4) carrying out high-temperature graphitization treatment on the high-density C/C composite material plate prepared in the step (S3), and then processing to obtain a C/C composite material bipolar plate semi-finished product;
and (S5) carrying out chemical vapor deposition pyrolytic carbon surface coating hole sealing on the semi-finished product of the C/C composite material bipolar plate prepared in the step (S4), and carrying out post-treatment to obtain the C/C composite material bipolar plate of the proton exchange membrane hydrogen fuel cell.
In one embodiment of the invention, the bipolar plate density of the C/C composite material of the proton exchange membrane hydrogen fuel cell is less than 2.0g/cm 3 The bending strength is more than 100MPa, the volume resistivity is less than 10 mu omega-m, and the corrosion current density is less than 1 mu A/cm 2 The air permeability is less than 2 multiplied by 10 -6 cm 3 /(s·cm 2 )。
In one embodiment of the present invention, in the step (S1), the carbon fiber preform is selected from one of a laminated carbon cloth or a carbon fiber web;
the Gao Cantan resin slurry is selected from one of phenolic resin, furfuryl ketone resin or boron phenolic resin;
the mass ratio of the carbon fiber preform to the high-carbon-residue resin slurry is 35-55: 45-65.
In one embodiment of the present invention, in the step (S1), the temperature is 100 to 300 ℃, the pressure is 50 to 200 tons, and the holding time is 1 to 3 hours during the compression molding and curing molding process.
In one embodiment of the invention, in the step (S2), the carbonization treatment process is carried out in an inert atmosphere environment, the temperature is 700-900 ℃, the pressure is 80-100 kPa, the heating rate is lower than 10 ℃/min, the cooling rate is lower than 15 ℃/min, and the heat preservation time is 1-10 h.
In one embodiment of the present invention, in step (S3), the high carbon residue slurry is a mixture of pitch and an organic solvent,
the organic solvent is selected from one of absolute ethyl alcohol and acetone;
in the high carbon residue slurry, the pitch accounts for 10 to 40 percent by weight.
In one embodiment of the present invention, in the step (S3), the impregnation densification process is performed in a vacuum environment, the number of impregnation densification is not less than 2, the vacuum melting temperature is 200 to 400 ℃, the carbonization temperature is 800 to 1000 ℃, and the pressure is 0.5 to 3MPa.
In one embodiment of the present invention, in the step (S4), the high temperature graphitization treatment process is performed under an inert atmosphere at a temperature of 2200 to 3000 ℃, a pressure of 80 to 100kPa, and a holding time of 1 to 10 hours.
In one embodiment of the present invention, in the step (S5), a mixed gas of one or more of natural gas, methane, propylene or propane is used as a precursor raw material in the hole sealing process of the chemical vapor deposition pyrolytic carbon surface coating;
the temperature is 1000-1100 ℃, the deposition pressure is 1-5 kPa, and the deposition time is 10-50 hours.
In one embodiment of the invention, the post-treatment is fine processing treatment according to the drawing requirements.
The second object of the invention is to provide a bipolar plate of a proton exchange membrane hydrogen fuel cell C/C composite material prepared by the method.
A third object of the present invention is to provide the use of a bipolar plate of a C/C composite material for a hydrogen fuel cell according to a proton exchange membrane for the preparation of a hydrogen fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
(1) The carbon fiber has good conductivity and high chemical stability, can meet the corrosion resistance performance requirement of the bipolar plate material, and can be used as a skeleton reinforcement to improve the bending strength of the C/C composite bipolar plate;
(2) The conductivity of the C/C composite bipolar plate can be obviously improved by means of asphalt impregnation densification and high-temperature heat treatment;
(3) The densified C/C composite bipolar plate is easy to process and light in weight, and can be thinned and weight-reduced.
Detailed Description
The invention provides a preparation method of a bipolar plate of a C/C composite material of a proton exchange membrane hydrogen fuel cell, which comprises the following steps:
(S1) carrying out compression molding, solidification and forming on a carbon fiber preform and high-carbon-residue resin slurry to obtain a resin-based composite material plate;
(S2) carbonizing the resin-based composite material plate prepared in the step (S1) to obtain a low-density C/C composite material plate;
(S3) carrying out impregnation densification on the low-density C/C composite material plate prepared in the step (S2) through high-carbon residue slurry to obtain a high-density C/C composite material plate;
(S4) carrying out high-temperature graphitization treatment on the high-density C/C composite material plate prepared in the step (S3), and then processing to obtain a C/C composite material bipolar plate semi-finished product;
and (S5) carrying out chemical vapor deposition pyrolytic carbon surface coating hole sealing on the semi-finished product of the C/C composite material bipolar plate prepared in the step (S4), and carrying out post-treatment to obtain the C/C composite material bipolar plate of the proton exchange membrane hydrogen fuel cell.
In one embodiment of the invention, the bipolar plate density of the C/C composite material of the proton exchange membrane hydrogen fuel cell is less than 2.0g/cm 3 The bending strength is more than 100MPa, the volume resistivity is less than 10 mu omega-m, and the corrosion current density is less than 1 mu A/cm 2 The air permeability is less than 2 multiplied by 10 -6 cm 3 /(s·cm 2 )。
In one embodiment of the present invention, in the step (S1), the carbon fiber preform is selected from one of a laminated carbon cloth or a carbon fiber web;
the Gao Cantan resin slurry is selected from one of phenolic resin, furfuryl ketone resin or boron phenolic resin;
the mass ratio of the carbon fiber preform to the high-carbon-residue resin slurry is 35-55: 45-65.
In one embodiment of the present invention, in the step (S1), the temperature is 100 to 300 ℃, the pressure is 50 to 200 tons, and the holding time is 1 to 3 hours during the compression molding and curing molding process.
In one embodiment of the invention, in the step (S2), the carbonization treatment process is carried out in an inert atmosphere environment, the temperature is 700-900 ℃, the pressure is 80-100 kPa, the heating rate is lower than 10 ℃/min, the cooling rate is lower than 15 ℃/min, and the heat preservation time is 1-10 h.
In one embodiment of the present invention, in step (S3), the high carbon residue slurry is a mixture of pitch and an organic solvent,
the organic solvent is selected from one of absolute ethyl alcohol and acetone;
in the high carbon residue slurry, the pitch accounts for 10 to 40 percent by weight.
In one embodiment of the present invention, in the step (S3), the impregnation densification process is performed in a vacuum environment, the number of impregnation densification is not less than 2, the vacuum melting temperature is 200 to 400 ℃, the carbonization temperature is 800 to 1000 ℃, and the pressure is 0.5 to 3MPa.
In one embodiment of the present invention, in the step (S4), the high temperature graphitization treatment process is performed under an inert atmosphere at a temperature of 2200 to 3000 ℃, a pressure of 80 to 100kPa, and a holding time of 1 to 10 hours.
In one embodiment of the present invention, in the step (S5), a mixed gas of one or more of natural gas, methane, propylene or propane is used as a precursor raw material in the hole sealing process of the chemical vapor deposition pyrolytic carbon surface coating;
the temperature is 1000-1100 ℃, the deposition pressure is 1-5 kPa, and the deposition time is 10-50 hours.
In one embodiment of the invention, the post-treatment is fine processing treatment according to the drawing requirements.
The invention provides a bipolar plate of a C/C composite material of a proton exchange membrane hydrogen fuel cell, which is prepared by the method.
The invention provides an application of a bipolar plate of a C/C composite material of a proton exchange membrane hydrogen fuel cell in preparing the hydrogen fuel cell.
The present invention will be described in detail with reference to specific examples.
In the examples below, unless otherwise specified, all reagents used were commercially available, and all detection means and methods used were conventional in the art.
Example 1
The embodiment provides a bipolar plate of a C/C composite material of a proton exchange membrane hydrogen fuel cell and a preparation method thereof, and the bipolar plate comprises the following steps:
(S1) selecting laminated carbon fiber cloth as a preform;
(S2) selecting phenolic resin as slurry;
(S3) carrying out compression molding, solidification and molding on 40wt% of the carbon fiber cloth preform in the step (S1) and 60wt% of the phenolic resin slurry in the step (S2) on a hot press at the temperature of 200 ℃, the pressure of 200 tons and the heat preservation time of 2 hours to obtain a resin-based composite material plate;
(S4) carbonizing the resin-based composite material plate in the step (S3) in nitrogen atmosphere at 800 ℃, under 100KPa, at a heating rate of 10 ℃/min, at a cooling rate of 15 ℃/min and for 10 hours, thereby obtaining a low-density C/C composite material plate;
(S5) preparing high-residue carbon slurry by 30wt% of asphalt and absolute ethyl alcohol, carrying out asphalt impregnation densification on the low-density C/C composite material plate in the step (S4) by using the high-residue carbon slurry, wherein the vacuum melting temperature is 400 ℃, the carbonization temperature is 800 ℃, the pressure is 3MPa, and the impregnation densification times are 3 times, so as to obtain the high-density C/C composite material plate;
(S6) carrying out high-temperature graphitization treatment on the high-density C/C composite material plate obtained in the step (S5) in a nitrogen atmosphere, wherein the temperature is 2600 ℃, the pressure is 100kPa, and the heat preservation time is 10 hours;
(S7) processing the graphitized high-density C/C composite material plate according to the size requirement of the bipolar plate to obtain a semi-finished product of the C/C composite material bipolar plate;
(S8) carrying out chemical vapor deposition pyrolysis carbon surface coating hole sealing on the bipolar plate semi-finished product, selecting natural gas as a precursor raw material, wherein the temperature is 1050 ℃, the deposition pressure is 3kPa, and the deposition time is 50 hours;
(S9) finely processing the bipolar plate semi-finished product subjected to coating hole sealing to ensure that the overall size and shape of the bipolar plate semi-finished product meet the requirements of a drawing, and finally obtaining the bipolar plate with the density of 1.6g/cm 3 The bending strength is 140MPa, the volume resistivity is 9 mu omega-m, and the corrosion current density is 0.8 mu A/cm 2 Air permeability 1.8X10 -6 cm 3 /(s·cm 2 ) A finished product of the C/C composite bipolar plate.
Example 2
This embodiment is substantially the same as embodiment 1, except that:
the high-temperature graphitization treatment temperature is 2800 ℃; final resultThe density was 1.65g/cm 3 The bending strength is 140MPa, the volume resistivity is 8 mu omega-m, and the corrosion current density is 0.8 mu A/cm 2 Air permeability 1.75X10 -6 cm 3 /(s·cm 2 ) A finished product of the C/C composite bipolar plate.
Example 3
This embodiment is substantially the same as embodiment 1, except that:
selecting 30wt% of carbon fiber net tire as a preform, wherein the number of times of asphalt impregnation densification is 4, and the temperature of high-temperature graphitization treatment is 3000 ℃; the final density was 1.7g/cm 3 130MPa bending strength, 6 mu omega-m volume resistivity and 0.7 mu A/cm corrosion current density 2 Air permeability 1.6X10 -6 cm 3 /(s·cm 2 ) A finished product of the C/C composite bipolar plate.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art, based on the explanation of the present invention, shall not depart from the technical principle and the inventive concept of the preparation method of the C/C composite bipolar plate of the proton exchange membrane hydrogen fuel cell according to the present invention as long as the present invention is in accordance with the purpose of the present invention.

Claims (10)

1. The preparation method of the bipolar plate of the C/C composite material of the proton exchange membrane hydrogen fuel cell is characterized by comprising the following steps:
(S1) carrying out compression molding, solidification and forming on a carbon fiber preform and high-carbon-residue resin slurry to obtain a resin-based composite material plate;
(S2) carbonizing the resin-based composite material plate prepared in the step (S1) to obtain a low-density C/C composite material plate;
(S3) carrying out impregnation densification on the low-density C/C composite material plate prepared in the step (S2) through high-carbon residue slurry to obtain a high-density C/C composite material plate;
(S4) carrying out high-temperature graphitization treatment on the high-density C/C composite material plate prepared in the step (S3), and then processing to obtain a C/C composite material bipolar plate semi-finished product;
and (S5) carrying out chemical vapor deposition pyrolytic carbon surface coating hole sealing on the semi-finished product of the C/C composite material bipolar plate prepared in the step (S4), and carrying out post-treatment to obtain the C/C composite material bipolar plate of the proton exchange membrane hydrogen fuel cell.
2. The method for producing a bipolar plate of a C/C composite material for a proton exchange membrane hydrogen fuel cell according to claim 1, wherein in the step (S1), the carbon fiber preform is one selected from a laminated carbon cloth and a carbon fiber web;
the Gao Cantan resin slurry is selected from one of phenolic resin, furfuryl ketone resin or boron phenolic resin;
the mass ratio of the carbon fiber preform to the high-carbon-residue resin slurry is 35-55: 45-65.
3. The method for preparing a bipolar plate of a proton exchange membrane hydrogen fuel cell C/C composite material according to claim 1, wherein in the step (S1), the temperature is 100-300 ℃, the pressure is 50-200 tons, and the heat preservation time is 1-3 hours in the compression molding and curing process.
4. The method for preparing a bipolar plate of a proton exchange membrane hydrogen fuel cell C/C composite material according to claim 1, wherein in the step (S2), the carbonization treatment process is carried out in an inert atmosphere environment, the temperature is 700-900 ℃, the pressure is 80-100 kPa, the heating rate is lower than 10 ℃/min, the cooling rate is lower than 15 ℃/min, and the heat preservation time is 1-10 h.
5. The method for preparing a bipolar plate of a proton exchange membrane hydrogen fuel cell C/C composite material according to claim 1, wherein in the step (S3), the high carbon residue slurry is a mixture of asphalt and an organic solvent,
the organic solvent is selected from one of absolute ethyl alcohol and acetone;
in the high carbon residue slurry, the pitch accounts for 10 to 40 percent by weight.
6. The method for preparing a bipolar plate of a proton exchange membrane hydrogen fuel cell C/C composite material according to claim 1, wherein in the step (S3), the impregnation densification process is carried out in a vacuum environment, the impregnation densification times are more than or equal to 2 times, the vacuum melting temperature is 200-400 ℃, the carbonization temperature is 800-1000 ℃, and the pressure is 0.5-3 MPa.
7. The method for preparing a bipolar plate of a proton exchange membrane hydrogen fuel cell C/C composite material according to claim 1, wherein in the step (S4), the high-temperature graphitization treatment process is carried out in an inert atmosphere, the temperature is 2200-3000 ℃, the pressure is 80-100 kPa, and the heat preservation time is 1-10 hours.
8. The method for preparing a bipolar plate of a proton exchange membrane hydrogen fuel cell C/C composite material according to claim 1, wherein in the step (S5), one or more mixed gases selected from natural gas, methane, propylene and propane are used as precursor raw materials in the process of sealing a hole in a chemical vapor deposition pyrolytic carbon surface coating;
the temperature is 1000-1100 ℃, the deposition pressure is 1-5 kPa, and the deposition time is 10-50 hours.
9. A proton exchange membrane hydrogen fuel cell C/C composite bipolar plate prepared by the method of any one of 1 to 8.
10. Use of a bipolar plate of a C/C composite material for a proton exchange membrane hydrogen fuel cell according to claim 9 for the production of a hydrogen fuel cell.
CN202311183178.XA 2023-09-14 2023-09-14 Proton exchange membrane hydrogen fuel cell C/C composite bipolar plate and preparation and application thereof Pending CN117239170A (en)

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CN202311183178.XA CN117239170A (en) 2023-09-14 2023-09-14 Proton exchange membrane hydrogen fuel cell C/C composite bipolar plate and preparation and application thereof

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Application Number Priority Date Filing Date Title
CN202311183178.XA CN117239170A (en) 2023-09-14 2023-09-14 Proton exchange membrane hydrogen fuel cell C/C composite bipolar plate and preparation and application thereof

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CN117239170A true CN117239170A (en) 2023-12-15

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