CN112952132B - PEM fuel cell, carbon-carbon composite bipolar plate and preparation method thereof - Google Patents

PEM fuel cell, carbon-carbon composite bipolar plate and preparation method thereof Download PDF

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CN112952132B
CN112952132B CN202110330391.3A CN202110330391A CN112952132B CN 112952132 B CN112952132 B CN 112952132B CN 202110330391 A CN202110330391 A CN 202110330391A CN 112952132 B CN112952132 B CN 112952132B
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bipolar plate
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李峰波
袁国卿
宋延林
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Institute of Chemistry CAS
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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
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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
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    • 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
    • H01M8/10—Fuel cells with solid electrolytes
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Abstract

The invention relates to a PEM fuel cell, a carbon-carbon composite bipolar plate and a preparation method thereof, belongs to the field of new energy and new materials, and solves the problems of poor conductivity, complex structure and high cost of the existing composite bipolar plate. The preparation method comprises the following steps: step 1, preparing a unidirectional PAN carbon fiber prefabricated film by using polyacrylonitrile carbon fibers and polyvinyl butyral; step 2, extracting and grading the coal tar pitch by using a toluene-benzyl alcohol mixed solvent, and performing high-temperature telomerization polymerization on the extracted polycyclic aromatic hydrocarbon mixture in the presence of elemental iodine to obtain a polycyclic aromatic hydrocarbon polycondensate; step 3, arranging the unidirectional PAN carbon fiber prefabricated film in an oriented manner and carrying out hot-press molding on the unidirectional PAN carbon fiber prefabricated film and the condensed-ring aromatic condensation polymer; and 4, carrying out high-temperature carbonization treatment on the carbon-carbon composite bipolar plate precursor obtained by hot press molding to obtain the carbon-carbon composite bipolar plate. The carbon-carbon composite bipolar plate has the advantages of high strength, high electric and heat conducting performance, good chemical stability and air tightness and low preparation cost.

Description

PEM fuel cell, carbon-carbon composite bipolar plate and preparation method thereof
Technical Field
The invention relates to the field of new energy and new materials, in particular to a PEM fuel cell, a carbon-carbon composite bipolar plate and a preparation method thereof.
Background
In Proton Exchange Membrane Fuel Cell (PEMFC) stacks, a bipolar plate is one of its core components, also commonly referred to as a current collector or separator plate.
The manufacturing cost of the bipolar plate accounts for 45-60% of the cost of the PEMFC pile, the weight of the bipolar plate accounts for 80% of the weight of the PEMFC pile, the high cost and the high weight ratio of the bipolar plate are one of the main obstacles for restricting the industrial application of the PEMFC at present, and the breakthrough and optimization of the bipolar plate material and the preparation process can greatly promote the industrial process of the PEMFC.
The bipolar plate may be classified into a graphite bipolar plate, a metal bipolar plate, and a composite bipolar plate according to the type of material. The graphite bipolar plate has the problems of high time consumption and cost of raw material treatment, fragile graphite material, poor processability and the like; the metal bipolar plate has the problems of poor corrosion resistance, sensitivity to the electrochemical process of an electrode, large contact resistance and the like; the composite bipolar plate has poor conductivity, complex structure and high cost.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a PEM fuel cell, a carbon-carbon composite bipolar plate and a preparation method thereof, so as to solve the problems of poor conductivity, complex structure and high cost of the existing composite bipolar plate.
The invention is mainly realized by the following technical scheme:
on one hand, the invention provides a carbon-carbon composite bipolar plate, and the preparation raw materials of the carbon-carbon composite bipolar plate comprise polyacrylonitrile carbon fibers, polyvinyl butyral, coal tar pitch, a toluene-benzyl alcohol mixed solvent and elemental iodine;
the mass ratio of the toluene-benzyl alcohol mixed solvent to the coal tar pitch is 3: 1-6: 1;
the volume ratio of toluene to benzyl alcohol in the toluene-benzyl alcohol mixed solvent is 1: 1-4: 1.
On the other hand, the invention also provides a preparation method of the carbon-carbon composite bipolar plate, which is used for preparing the carbon-carbon composite bipolar plate and comprises the following steps:
step 1, preparing a unidirectional PAN carbon fiber prefabricated film by using polyacrylonitrile carbon fibers and polyvinyl butyral;
step 2, performing solvent extraction and grading treatment on the coal tar pitch by using a toluene-benzyl alcohol mixed solvent to obtain a polycyclic aromatic hydrocarbon mixture; carrying out high-temperature telomerization polymerization on the polycyclic aromatic hydrocarbon mixture in the presence of elemental iodine to prepare a polycyclic aromatic hydrocarbon polycondensate;
step 3, the unidirectional PAN carbon fiber prefabricated film prepared in the step 1 is arranged according to the orientation of 0-90 ° - +45 ° - +45 ° -90 ° -0 °, and is subjected to hot press molding with the condensed ring aromatic hydrocarbon polycondensate prepared in the step 2 after arrangement to prepare a carbon-carbon composite bipolar plate precursor;
and 4, performing high-temperature carbonization treatment on the carbon-carbon composite bipolar plate precursor to prepare the all-carbon-carbon composite bipolar plate.
Further, in the step 1, the polyacrylonitrile carbon fiber is heated in the air at 350-450 ℃ for 10-50 min;
and (3) soaking the heated polyacrylonitrile carbon fiber in a polyvinyl butyral ethanol solution with the mass concentration of 0.4-4%, arranging the polyacrylonitrile carbon fiber on a polytetrafluoroethylene substrate, and preparing the unidirectional PAN carbon fiber prefabricated film after ethanol is completely volatilized.
Further, in the step 1, the length of the polyacrylonitrile carbon fiber is 5.0-50 mm;
the areal density of the unidirectional PAN carbon fiber prefabricated film is 5.0-50 mg/cm2。
Further, in the step 2, the temperature of the solvent extraction and classification treatment is 40-90 ℃, the treatment time is 30-180 min, and the mechanical stirring speed adopted in the treatment process is 90-300 r/min; and after the solvent extraction and classification treatment is finished, separating the solvent by adopting reduced pressure distillation to obtain a polycyclic aromatic hydrocarbon mixture.
Further, in the step 2, the high-temperature telomerization polymerization temperature is 120-350 ℃, and the high-temperature telomerization polymerization time is 0.5-4.5 h;
the molar ratio of iodine elements in the elementary iodine to carbon elements in the polycyclic aromatic hydrocarbon mixture is 0.005-0.045.
Further, in the step 2, in the fused ring aromatic hydrocarbon mixture, the number of carbons of the average molecular total aromatic ring is 24.2-29.0, and the average molecular total aromatic ring is 6.0-7.8.
Further, in step 3, the polycyclic aromatic hydrocarbon condensation polymer is arranged above the unidirectional PAN carbon fiber prefabricated film during hot press molding; the hot press molding temperature is 150-260 ℃;
the mass ratio of the unidirectional PAN carbon fiber prefabricated film to the condensed ring aromatic condensation polymer is 0.2-3.0.
Further, in the step 4, the temperature rise rate of the high-temperature carbonization treatment is 1.0-10 ℃/min, the carbonization treatment temperature is 850-1200 ℃, and the carbonization treatment time is 0.6-6.0 h;
the flow of argon in the high-temperature carbonization treatment process is 50-700 ml/min.
Furthermore, the invention also provides a PEM fuel cell, which comprises the carbon-carbon composite bipolar plate; or the carbon-carbon composite bipolar plate prepared by the preparation method of the carbon-carbon composite bipolar plate.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) the carbon-carbon composite bipolar plate is characterized in that the carbon-carbon composite material consists of regularly arranged carbon fibers and a pyrolytic carbon matrix generated by condensation polymer of polycyclic aromatic hydrocarbon, so that the carbon-carbon bipolar plate has excellent electrical conductivity. The composite structure formed by the carbon fibers and the pyrolytic carbon matrix has excellent heat conduction performance, and heat exchange generated by the PEM battery unit is facilitated to be conducted out of the system, so that the temperature of the battery system is kept stable.
(2) The carbon-carbon composite bipolar plate is a composite structure formed by regularly arranged carbon fibers and a pyrolytic carbon matrix, and has good mechanical properties (the tensile strength is up to 138MPa, and the elongation at break is up to 4.1 percent) due to the close combination of the carbon fibers and the pyrolytic carbon matrix (the carbon fibers and the pyrolytic carbon matrix adopt physical embedding and interface chemical bonding interaction, and are specifically reflected on the amphoteric parameters of the tensile strength and the elongation at break of the material), and meanwhile, the carbon-carbon composite bipolar plate has lower density which is about 30 percent lower than that of the bipolar plate material in the prior art.
(3) The full-carbon-carbon composite bipolar plate provided by the invention has stable chemical properties, so that the full-carbon-carbon composite bipolar plate has good corrosion resistance; the carbon-carbon composite bipolar plate is obtained by high-temperature carbonization (850-1200 ℃), and has high purity and extremely low volatile components (VOCs) or extractable components (EOCs).
(4) The carbon-carbon composite material bipolar plate is formed by one-step hot press molding, and the forming process is simple and short in production period. The bipolar plate prepared from the carbon-carbon composite material has low process cost and high efficiency, and is beneficial to realizing the light weight, the miniaturization and the thinning of the battery.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a schematic diagram showing the mechanism of promotion of high-temperature polymerization of a fused-ring aromatic hydrocarbon mixture by iodine;
FIG. 2 is a schematic view of the unidirectional PAN carbon fiber preform film aligned at an orientation of 0 ° -90 ° -45 ° -90 ° -0 °;
fig. 3 is a schematic view illustrating a process of forming a carbon-carbon composite bipolar plate (carbon fiber-pyrolytic carbon matrix composite structure);
fig. 4 is a schematic view of a carbon-carbon composite bipolar plate.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention and not to limit its scope.
In one aspect, the present invention provides a carbon-carbon composite bipolar plate, as shown in fig. 4, for manufacturing a PEM fuel cell, the carbon-carbon composite bipolar plate is prepared from the following raw materials: polyacrylonitrile (PAN) carbon fibers (PAN carbon fibers), polyvinyl butyral (PVB), coal tar pitch, a toluene-benzyl alcohol mixed solvent and elemental iodine.
Wherein Polyacrylonitrile (PAN) carbon fiber is the fiber of the carbon-carbon composite material bipolar plate; polyvinyl butyral (PVB) is a binder of the unidirectional PAN carbon fiber prefabricated film; the coal tar pitch dissolved in the toluene-benzyl alcohol mixed solvent is a condensed ring aromatic hydrocarbon mixture, and the condensed ring aromatic hydrocarbon mixture is a raw material monomer of a condensed ring aromatic hydrocarbon polycondensate for preparing the carbon-carbon composite bipolar plate precursor; the carbon number of the total aromatic rings of the average molecules in the mixture of the polycyclic aromatic hydrocarbons is 24.2-29.0, and the total number of the aromatic rings of the average molecules is 6.0-7.8; the elementary iodine is an accelerant for high-temperature telomerization and polymerization of a fused ring aromatic hydrocarbon mixture.
The Polyacrylonitrile (PAN) carbon fiber adopts a commercial product, and the technical parameters are as follows: the number of the filament bundles is 6 to 24K, the density is 1.73 to 1.96, the tensile strength is 2700 to 6370, and the tensile modulus is 230 to 580.
The technical indexes of the coal tar pitch raw material are specified by the national standard GB/T2290-. In order to obtain a carbon matrix precursor material suitable for preparing a carbon-carbon composite material, the coal tar pitch is subjected to toluene-benzyl alcohol extraction and classification treatment to obtain a condensed ring aromatic hydrocarbon mixture with average molecular total aromatic ring carbon number of 24.2-29.0 and average molecular total aromatic ring number of 6.0-7.8, wherein the volume ratio of a toluene-benzyl alcohol mixed solvent to a toluene-benzyl alcohol mixed solvent is 1: 1-4: 1. The solvent is separated out by reduced pressure distillation, and the polycyclic aromatic hydrocarbon mixture is further subjected to high-temperature telomerization.
The high-temperature telomerization polymerization temperature is 150-260 ℃, the elemental iodine is used as an accelerant in the high-temperature telomerization process, and the molar ratio of iodine element to carbon element is 0.005-0.045. After the high-temperature telomerization is finished, removing excessive elemental iodine by using ethanol; in the elementary iodine participating in the reaction, iodine atoms and aromatic hydrocarbon condensed rings react to generate halogenated groups, and such heteroatoms can promote the polymerization and aromatization of a carbon structure in the high-temperature carbonization process, so that the yield and graphitization degree in the high-temperature carbonization process are improved.
The unidirectional PAN carbon fiber prefabricated film is arranged according to the orientation of 0-90-45-90-0 degrees, a fused ring aromatic hydrocarbon condensation polymer obtained by high-temperature telomerization and polymerization is fully impregnated with the unidirectional PAN carbon fiber prefabricated film, the mass ratio of the unidirectional PAN carbon fiber prefabricated film to the high-temperature telomerization fused ring aromatic hydrocarbon condensation polymer is 0.2-3.0, and the impregnated compound is further subjected to hot press molding to obtain the carbon-carbon composite bipolar plate precursor. And carrying out high-temperature carbonization treatment on the carbon-carbon composite bipolar plate precursor in argon gas flow at 850-1200 ℃ to finally obtain the full-carbon-carbon composite bipolar plate.
The carbon-carbon composite material bipolar plate material provided by the invention has the following properties: 1) has high conductivity; 2) is hotA good conductor; 3) high mechanical strength (tensile strength up to 138 MPa); 4) light weight and good processability, 5) good corrosion resistance, stability and operating life; 6) has good gas tightness (by hydrogen permeability (cm)3·sec-1·cm-2) The hydrogen permeability of the invention is measured to be as high as 3.2 multiplied by 10-5cm3·sec-1·cm-2) High purity and extremely low volatile components (VOCs) or extractable components (EOCs) (the bipolar plate material of the invention is prepared by high-temperature treatment at 850-1200 ℃, so the purity is high); 7) good mechanical and chemical compatibility with a Gas Diffusion Layer (GDL) (the gas diffusion layer is porous carbon paper, the bipolar plate of the invention is a carbon-carbon composite material, and the porous carbon paper and the bipolar plate have good mechanical and chemical compatibility), and higher surface flatness (the surface roughness is less than or equal to 7 mu m).
In another aspect, the present invention further provides a method for preparing a carbon-carbon composite bipolar plate, which is used for preparing the carbon-carbon composite bipolar plate, and the carbon-carbon composite bipolar plate is used in a PEM fuel cell, and the method for preparing the carbon-carbon composite bipolar plate comprises the following steps:
step 1, preparing a unidirectional PAN carbon fiber prefabricated film by using Polyacrylonitrile (PAN) carbon fibers and polyvinyl butyral (PVB);
step 2, extracting and grading coal tar pitch by adopting a toluene-benzyl alcohol mixed solvent to obtain a polycyclic aromatic hydrocarbon mixture, and carrying out high-temperature telomerization on the polycyclic aromatic hydrocarbon mixture in the presence of elemental iodine to prepare a polycyclic aromatic hydrocarbon polycondensate (namely an isotropic pitch polymer mixture);
step 3, carrying out hot-press molding on the unidirectional PAN carbon fiber prefabricated film and the condensed ring aromatic condensation polymer to prepare a carbon-carbon composite bipolar plate precursor;
and 4, performing high-temperature carbonization treatment on the carbon-carbon composite bipolar plate precursor to prepare the all-carbon-carbon composite bipolar plate.
Specifically, in the step 1, the length of Polyacrylonitrile (PAN) carbon fiber is 5.0-50 mm; firstly, heating Polyacrylonitrile (PAN) carbon fiber in air at 350-450 DEG CTreating for 10-50 min, then adopting a polyvinyl butyral (PVB) ethanol solution with the mass concentration of 0.4-4% to dip the Polyacrylonitrile (PAN) carbon fibers subjected to heating treatment, using the PVB as a binder to arrange the Polyacrylonitrile (PAN) carbon fibers on a polytetrafluoroethylene substrate, and finally completely volatilizing ethanol in the air to prepare the unidirectional PAN carbon fiber prefabricated film, wherein the areal density of the unidirectional PAN carbon fiber prefabricated film is 5.0-50 mg/cm2。
In the step 1, Polyacrylonitrile (PAN) carbon fiber is treated in air at 350-450 ℃ for 10-50 min to remove a high molecular finishing agent (generally one or a mixture of polyhydroxy ether, polyphenyl ether, styrene maleic anhydride copolymer and silicone) on the surface of the Polyacrylonitrile (PAN) carbon fiber, and to oxidize the surface to introduce some functional groups to increase the interaction between the Polyacrylonitrile (PAN) carbon fiber and the soaked polyvinyl butyral (PVB) ethanol solution.
In the step 2, coal tar pitch is dissolved in a toluene-benzyl alcohol mixed solvent, and then extraction and classification treatment is carried out, wherein the mechanical stirring speed adopted in the classification treatment process is 90-300 r/min, so as to obtain a condensed ring aromatic hydrocarbon mixture with the average molecular total aromatic ring carbon number of 24.2-29.0 and the average molecular total aromatic ring number of 6.0-7.8; the carbon number of the aromatic ring and the total number of the aromatic ring are controlled within the range, so that a fused ring aromatic hydrocarbon mixture with proper molecular weight distribution, boiling point range and reaction activity is obtained.
The mass ratio of the toluene-benzyl alcohol mixed solvent to the coal tar pitch is 3: 1-6: 1, the volume ratio of toluene to benzyl alcohol in the toluene-benzyl alcohol mixed solvent is 1: 1-4: 1, the extraction and classification temperature is 40-90 ℃, and the classification time is 30-180 min; the mass ratio of the toluene-benzyl alcohol mixed solvent to the coal tar pitch is controlled within the range of 3: 1-6: 1, so that components meeting the requirement can be fully extracted, the components are insufficiently mixed in the extraction process when the ratio is too low, and the energy consumption of the post-treatment process can be increased due to excessive solvent when the ratio is too high.
The volume ratio of the toluene to the benzyl alcohol in the toluene-benzyl alcohol mixed solvent is controlled within the range of 1: 1-4: 1, so that the polarity and the dissolving performance of the extraction solvent can be adjusted, and the extraction solvent is suitable for dissolving components suitable for requirements. Furthermore, the extraction and grading treatment temperature is 40-90 ℃, the grading treatment time is 30-180 min, the maximum efficiency of the extraction process is favorably realized, and the extraction temperature is more than 90 ℃, so that the selectivity of the extraction process is reduced.
In the step 2, after the extraction and grading treatment, the solvent is separated by reduced pressure distillation, the vacuum degree of the reduced pressure distillation is-0.05-0 MPa, and the reduced pressure distillation temperature is 60-80 ℃, so that the fused ring aromatic hydrocarbon mixture with proper molecular weight distribution (namely, the conditions that the carbon number of the total aromatic rings of the average molecules is 24.2-29.0 and the total number of the aromatic rings of the average molecules is 6.0-7.8) is prepared.
Directly mix above-mentioned polycyclic aromatic hydrocarbon mixture and elementary substance iodine and obtain the mixture, the iodine element in the mixture is 0.005 ~ 0.045 with the molar ratio of carbon element, is favorable to realizing the polymerization of iodine catalysis fused ring, and iodine element/carbon element ratio is low can not play catalytic effect excessively, and iodine element/carbon element's ratio too high can cause telomerization polymerization process uncontrollable, also can make the iodine residue volume too high simultaneously. And carrying out high-temperature telomerization polymerization on the mixture at the temperature of 120-350 ℃, wherein the high-temperature telomerization polymerization time is 0.5-4.5 h, so as to improve the polymerization degree of the polycyclic aromatic hydrocarbon mixture.
After the high-temperature telomerization polymerization is finished, ethanol solution with the volume 1.5-3.5 times of that of the mixture after the high-temperature telomerization polymerization is adopted to leach redundant elementary iodine, part of iodine atoms (part of iodine atoms refer to iodine elements participating in aromatic hydrocarbon condensed ring reaction) and aromatic hydrocarbon condensed rings react to generate halogenated groups, and the heteroatoms can promote polymerization and aromatization of a carbon structure in the high-temperature carbonization process, so that the yield and graphitization degree of the high-temperature carbonization process can be improved, wherein the promotion action mechanism of the iodine elements on the high-temperature carbonization process is shown in fig. 1.
In the step 3, the unidirectional PAN carbon fiber prefabricated film is arranged according to the orientation of 0-90 degrees to +45 degrees to-45 degrees to +45 degrees to-90 degrees to 0 degrees, and an isotropic fiber structure can be obtained by adopting the specific arrangement orientation, so that the internal structural difference of the material is avoided. As shown in fig. 2, the unidirectional PAN carbon fiber prefabricated film is arranged and then is hot-pressed with a condensed-ring aromatic polycondensate to prepare a carbon-carbon composite bipolar plate precursor; wherein the hot-press molding temperature is 150-260 ℃, and the mass ratio of the unidirectional PAN carbon fiber prefabricated film to the polycyclic aromatic hydrocarbon polycondensate is 0.2-3.0.
It is emphasized that when the unidirectional PAN carbon fiber prefabricated film is formed by hot pressing with the high-temperature telomerization condensed ring aromatic hydrocarbon condensation polymer, the condensed ring aromatic hydrocarbon condensation polymer is arranged above the unidirectional PAN carbon fiber prefabricated film, and the condensed ring aromatic hydrocarbon condensation polymer gradually permeates into the pore structure of the unidirectional PAN carbon fiber prefabricated film under the action of pressure and high temperature.
In the step 3, the mass ratio of the unidirectional PAN carbon fiber prefabricated film to the polycyclic aromatic hydrocarbon mixture is controlled within the range of 0.2-3.0, which is favorable for forming the carbon-carbon composite bipolar plate precursor with the density and strength meeting the requirements, and the content of pyrolytic carbon in the carbon-carbon composite bipolar plate precursor is higher due to too low mass ratio, so that the mechanical property of the carbon-carbon composite bipolar plate precursor is reduced; and too high a mass ratio may cause defects in the carbon-carbon composite bipolar plate precursor.
In the step 4, performing high-temperature carbonization treatment on the carbon-carbon composite bipolar plate precursor, heating the carbon-carbon composite bipolar plate precursor by using a tube furnace, supporting the carbon-carbon composite bipolar plate precursor by using a pure nickel foil, taking argon as a carrier gas, heating to 850-1200 ℃ at a heating rate of 1.0-10 ℃/min, and performing high-temperature carbonization treatment for 0.6-6.0 h; the flow of argon in the carbonization treatment process is 50-700 ml/min. The high-temperature carbonization treatment condition is controlled within the range, so that the generation of a pyrolytic carbon structure is facilitated, and the unevenness of a micro-area structure caused by the high-temperature carbonization process is avoided, so that the interaction force between the carbon fiber and the pyrolytic carbon substrate is reduced. A schematic diagram of the formation process of the carbon-carbon composite (carbon fiber/pyrolytic carbon matrix composite structure) bipolar plate is shown in fig. 3.
Compared with the prior art, the invention adopts the carbon-carbon composite material with full carbon as the bipolar plate, and the carbon-carbon composite material is composed of carbon fibers which are regularly arranged and a carbon matrix generated by pyrolyzing the polycyclic aromatic hydrocarbon mixture, and has excellent electrical conductivity and thermal conductivity. The carbon-carbon composite material bipolar plate has good mechanical property and lower density; the full-carbonaceous carbon-carbon composite bipolar plate has stable chemical properties, thereby having good corrosion resistance; the carbon-carbon composite material bipolar plate is formed by one-step hot pressing, the forming process is simple, the production period is short, the preparation process cost is controllable, and the miniaturization and thinning of the bipolar plate are favorably realized.
Moreover, the invention also provides a PEM fuel cell which adopts the carbon-carbon composite bipolar plate. The air chamber of the PEM fuel cell is composed of carbon-carbon composite bipolar plates, and is distributed on two sides of the galvanic pile unit, one side is a hydrogen chamber, the other side is an oxygen chamber, and a cooling pipeline is arranged in the middle of the carbon-carbon composite bipolar plates. The carbon-carbon composite bipolar plate has flow field channels for introducing fuel gas into the electrochemical reaction cells of the fuel cell. Meanwhile, the carbon-carbon composite bipolar plate also plays a role in isolating and sealing gas; providing conductive connection and current output for the multi-stage fuel cell units in the stack; providing a cooling liquid flow for the fuel cell unit, and exchanging heat generated by the electrochemical process to the outside of the system so as to keep the temperature of the system stable; effectively discharging water generated in the electrode reaction process out of the battery unit in time, and simultaneously keeping the battery unit at proper humidity; providing structural support, reactant flow isolation, and stack compressive loading for the fuel cell unit.
Example 1
The embodiment provides a preparation method of a carbon-carbon composite bipolar plate, and the prepared carbon-carbon composite bipolar plate is used for a PEM fuel cell, and the preparation method comprises the following steps:
step 1, preparing a unidirectional PAN carbon fiber prefabricated film by using Polyacrylonitrile (PAN) carbon fibers and polyvinyl butyral (PVB);
treating 8.0g of Polyacrylonitrile (PAN) carbon fiber in air at 420 ℃ for 30min, and preparing a unidirectional PAN carbon fiber prefabricated film (20 x 20cm) on a polytetrafluoroethylene substrate by using polyvinyl butyral (PVB) as a binder after treatment, wherein the parameters of the unidirectional PAN carbon fiber prefabricated film are shown in Table 1 (the length refers to the length of the unidirectional PAN carbon fiber prefabricated film).
PAN carbon fibers were impregnated and aligned with 20ml of a polyvinyl butyral (PVB) ethanol solution having a mass concentration of 2.0%.
Step 2, extracting and grading the coal tar pitch by adopting a toluene-benzyl alcohol mixed solvent to obtain a polycyclic aromatic hydrocarbon mixture, and carrying out high-temperature telomerization on the polycyclic aromatic hydrocarbon mixture in the presence of elemental iodine to prepare a polycyclic aromatic hydrocarbon mixture (namely an isotropic pitch polymer mixture);
mixing 100g of coal tar pitch and 450g of toluene-benzyl alcohol (2:1, V/V) mixed solvent, extracting and treating for 90min under mechanical stirring at 50 ℃ and 160r/min, separating out insoluble substances, and performing reduced pressure distillation (-0.03MPa, 70 ℃) on the remaining liquid phase mixture to separate out the solvent, thereby preparing the polycyclic aromatic hydrocarbon mixture.
Directly mixing the fused ring aromatic hydrocarbon mixture with elemental iodine to obtain a mixture of the fused ring aromatic hydrocarbon mixture and the elemental iodine, wherein the molar ratio of iodine elements to carbon elements is 0.025, and carrying out high-temperature telomerization polymerization on the mixture of the fused ring aromatic hydrocarbon mixture and the elemental iodine at the reaction temperature of 240 ℃ for 2.0 h. After the high-temperature telomerization is finished, 2.5 times of ethanol is adopted to leach redundant elementary iodine.
And 3, carrying out hot-press molding on the unidirectional PAN carbon fiber prefabricated film and the fused ring aromatic hydrocarbon mixture to prepare the carbon-carbon composite bipolar plate precursor.
Arranging the unidirectional PAN carbon fiber PVB prefabricated film according to the orientation of 0-90 to +45 to-45 to +45 to-90 to-0, and performing hot press molding on the arranged film and a high-temperature telomerized fused ring aromatic hydrocarbon mixture to prepare a carbon-carbon composite bipolar plate precursor, wherein the hot press molding temperature is 210 ℃. Wherein the mass ratio of the unidirectional PAN carbon fiber prefabricated film to the high-temperature telomerized polycyclic aromatic hydrocarbon mixture is 1.6.
And 4, performing high-temperature carbonization treatment on the carbon-carbon composite bipolar plate precursor to prepare the all-carbon-carbon composite bipolar plate.
The precursor of the carbon-carbon composite bipolar plate is subjected to high-temperature carbonization treatment, a tubular furnace is adopted for heating, a pure nickel foil is adopted for supporting the carbon-carbon composite bipolar plate, argon is used as carrier gas, the temperature is increased to 1000 ℃ at the temperature rise rate of 5.0 ℃/min, and the carbonization treatment time is 3.0 h. The flow of argon in the high-temperature carbonization treatment process is 260ml/min, so that the carbon-carbon composite material bipolar plate is prepared.
TABLE 1 relationship between parameters of unidirectional PAN carbon fiber prefabricated membrane and bipolar plate properties
Figure BDA0002989173770000121
Example 2
The embodiment provides a preparation method of a carbon-carbon composite bipolar plate, and the prepared carbon-carbon composite bipolar plate is used for a PEM fuel cell, and the preparation method comprises the following steps:
step 1, preparing a unidirectional PAN carbon fiber prefabricated film by using Polyacrylonitrile (PAN) carbon fibers and polyvinyl butyral (PVB);
8.0g of Polyacrylonitrile (PAN) carbon fiber is taken and treated for 30min in the air at the temperature of 420 ℃, and the length of the Polyacrylonitrile (PAN) carbon fiber is 20 mm. The PAN carbon fiber is prepared into a unidirectional PAN carbon fiber prefabricated film (20 multiplied by 20cm) on a polytetrafluoroethylene substrate by using polyvinyl butyral (PVB) as a binder, and the areal density of the unidirectional PAN carbon fiber prefabricated film is 21mg/cm2。
PAN carbon fibers are impregnated in 20ml of polyvinyl butyral (PVB) ethanol solution for arrangement, and the mass concentration of the polyvinyl butyral (PVB) ethanol solution is 2.0%.
Step 2, extracting and grading coal tar pitch by using a toluene-benzyl alcohol mixed solvent to obtain a condensed ring aromatic hydrocarbon mixture, and carrying out high-temperature telomerization polymerization on the condensed ring aromatic hydrocarbon mixture in the presence of elemental iodine to prepare a condensed ring aromatic hydrocarbon mixture (namely an isotropic pitch polymer mixture);
specifically, 100g of coal tar pitch is mixed with 450g of toluene-benzyl alcohol (2:1, V/V) solvent, extraction treatment is carried out for 90min under the conditions of 50 ℃ and 160r/min of rotation speed and mechanical stirring, insoluble substances are separated, and the remaining liquid phase mixture is subjected to reduced pressure distillation (-0.03MPa, 70 ℃) to separate the solvent, so that the polycyclic aromatic hydrocarbon mixture is prepared.
Directly mixing a fused ring aromatic hydrocarbon mixture with elemental iodine to obtain a mixture of the fused ring aromatic hydrocarbon mixture and the elemental iodine, and carrying out high-temperature telomerization on the mixture at a higher reaction temperature, wherein parameters involved in the high-temperature telomerization process are listed in a table 2, wherein I/C refers to the molar ratio of iodine elements to carbon elements. After the high-temperature telomerization is finished, 2.5 times of ethanol is adopted to leach redundant elementary iodine.
And 3, carrying out hot-press molding on the unidirectional PAN carbon fiber prefabricated film and the fused ring aromatic hydrocarbon mixture to prepare the carbon-carbon composite bipolar plate precursor.
Arranging the unidirectional PAN carbon fiber PVB prefabricated film according to the orientation of 0-90 to +45 to-45 to +45 to-90 to-0, and performing hot press molding on the arranged film and a fused ring aromatic condensation polymer prepared by high-temperature telomerization to prepare a carbon-carbon composite bipolar plate precursor, wherein the hot press molding temperature is 210 ℃. Wherein the mass ratio of the unidirectional PAN carbon fiber prefabricated film to the polycyclic aromatic hydrocarbon mixture prepared by high-temperature telomerization is 1.6.
And 4, performing high-temperature carbonization treatment on the carbon-carbon composite bipolar plate precursor to prepare the all-carbon-carbon composite bipolar plate.
The carbon-carbon composite material PEMFC bipolar plate precursor is subjected to high-temperature carbonization treatment, a tube furnace is adopted for heating, a pure nickel foil is adopted for supporting the carbon-carbon composite material bipolar plate, argon is used as carrier gas, the temperature is increased to 1000 ℃ at the temperature increase rate of 5.0 ℃/min, and the carbonization treatment time is 3.0 h. The flow of argon in the high-temperature carbonization treatment process is 260ml/min, so that the carbon-carbon composite material bipolar plate is prepared.
TABLE 2 influence of high-temperature telomerization process parameters of polycyclic aromatic hydrocarbon mixtures and elemental iodine on bipolar plate performance
Figure BDA0002989173770000141
Figure BDA0002989173770000151
Example 3
The embodiment provides a preparation method of a carbon-carbon composite bipolar plate, and the prepared carbon-carbon composite bipolar plate is used for a PEM fuel cell, and the preparation method comprises the following steps:
step 1, preparing a unidirectional PAN carbon fiber prefabricated film by using Polyacrylonitrile (PAN) carbon fibers and polyvinyl butyral (PVB);
8.0g of Polyacrylonitrile (PAN) carbon fiber is taken and treated for 30min in the air at the temperature of 420 ℃, and the length of the Polyacrylonitrile (PAN) carbon fiber is 20 mm. The PAN carbon fiber is prepared into a unidirectional PAN carbon fiber prefabricated film (20 multiplied by 20cm) on a polytetrafluoroethylene substrate by using polyvinyl butyral (PVB) as a binder, and the areal density of the unidirectional PAN carbon fiber prefabricated film is 21mg/cm2. The PAN carbon fiber array was impregnated with 20ml of a polyvinyl butyral (PVB) ethanol solution having a mass concentration of 2.0%.
Step 2, extracting and grading coal tar pitch by using a toluene-benzyl alcohol mixed solvent to obtain a condensed ring aromatic hydrocarbon mixture, and carrying out high-temperature telomerization polymerization on the condensed ring aromatic hydrocarbon mixture in the presence of elemental iodine to prepare a condensed ring aromatic hydrocarbon mixture (namely an isotropic pitch polymer mixture);
mixing 100g of coal tar pitch and 450g of toluene-benzyl alcohol (2:1, V/V) mixed solvent, extracting and treating for 90min under mechanical stirring at 50 ℃ and 160r/min, separating out insoluble substances, and performing reduced pressure distillation (-0.03MPa, 70 ℃) on the remaining liquid phase mixture to separate out the solvent, thereby preparing the polycyclic aromatic hydrocarbon mixture.
Directly mixing a fused ring aromatic hydrocarbon mixture with elemental iodine, wherein the molar ratio (I/C) of iodine elements to carbon elements is 0.025, and carrying out high-temperature telomerization polymerization on the mixture at a higher reaction temperature of 240 ℃ for 2.0 h. After the high-temperature telomerization is finished, 2.5 times of ethanol is adopted to leach redundant elementary iodine.
And 3, carrying out hot-press molding on the unidirectional PAN carbon fiber prefabricated film and the fused ring aromatic hydrocarbon mixture to prepare the carbon-carbon composite bipolar plate precursor.
The unidirectional PAN carbon fiber PVB prefabricated film is arranged according to the orientation of 0-90-45-90-0 degrees, and is hot-pressed and formed with a condensed ring aromatic hydrocarbon polycondensate prepared by high-temperature telomerization after being arranged, so that the carbon-carbon composite bipolar plate precursor is prepared (the parameters of the hot-pressing and forming process are listed in a table 3, and the hot-pressing and forming ratio in the table refers to the mass ratio of the unidirectional PAN carbon fiber prefabricated film to the condensed ring aromatic hydrocarbon polycondensate).
And 4, performing high-temperature carbonization treatment on the carbon-carbon composite bipolar plate precursor to prepare the all-carbon-carbon composite bipolar plate.
Carbonizing the carbon-carbon composite bipolar plate precursor, heating by adopting a tube furnace, supporting the carbon-carbon composite bipolar plate precursor by adopting a pure nickel foil, taking argon as a carrier gas, heating to 1000 ℃ at the heating rate of 5.0 ℃/min, and carrying out high-temperature carbonization for 3.0 h. The flow rate of argon in the carbonization treatment process is 260ml/min, so that the carbon-carbon composite material bipolar plate is prepared.
TABLE 3 Effect of Hot Press Molding Process parameters on Bipolar plate Performance
Figure BDA0002989173770000161
Figure BDA0002989173770000171
Example 4
The embodiment provides a preparation method of a carbon-carbon composite PEM fuel cell bipolar plate, which comprises the following steps:
step 1, preparing a unidirectional PAN carbon fiber prefabricated film by using Polyacrylonitrile (PAN) carbon fibers and polyvinyl butyral (PVB);
8.0g of Polyacrylonitrile (PAN) carbon fiber is taken and treated in the air at 420 ℃ for 30min, and the length of the Polyacrylonitrile (PAN) carbon fiber is 20 mm. The PAN carbon fiber is prepared into a unidirectional PAN carbon fiber prefabricated film (20 multiplied by 20cm) on a polytetrafluoroethylene substrate by using polyvinyl butyral (PVB) as a binder, and the areal density of the unidirectional PAN carbon fiber prefabricated film is 21mg/cm2。
The PAN carbon fiber array was impregnated with 20ml of a polyvinyl butyral (PVB) ethanol solution having a mass concentration of 2.0%.
Step 2, extracting and grading coal tar pitch by using a toluene-benzyl alcohol mixed solvent to obtain a condensed ring aromatic hydrocarbon mixture, and carrying out high-temperature telomerization polymerization on the condensed ring aromatic hydrocarbon mixture in the presence of elemental iodine to prepare a condensed ring aromatic hydrocarbon mixture (namely an isotropic pitch polymer mixture);
mixing 100g of coal tar pitch and 450g of toluene-benzyl alcohol (2:1, V/V) mixed solvent, extracting and treating for 90min under mechanical stirring at 50 ℃ and 160r/min, separating out insoluble substances, and performing reduced pressure distillation (-0.03MPa, 70 ℃) on the remaining liquid phase mixture to separate out the solvent, thereby preparing the polycyclic aromatic hydrocarbon mixture.
Directly mixing a fused ring aromatic hydrocarbon mixture with elemental iodine, wherein the molar ratio of iodine element to carbon element is 0.025, and carrying out high-temperature telomerization polymerization on the mixture at a higher reaction temperature of 240 ℃, wherein the time of the high-temperature telomerization polymerization is 2.0 h; after the telomerization is completed, 2.5 times of ethanol is used for leaching redundant elementary iodine.
And 3, carrying out hot-press molding on the unidirectional PAN carbon fiber prefabricated film and the fused ring aromatic hydrocarbon mixture to prepare the carbon-carbon composite bipolar plate precursor.
Arranging the unidirectional PAN carbon fiber PVB prefabricated film according to the orientation of 0-90 to +45 to-45 to +45 to-90 to-0, and performing hot press molding on the arranged film and a condensed ring aromatic hydrocarbon polycondensate prepared by high-temperature telomerization to prepare a carbon-carbon composite bipolar plate precursor, wherein the hot press molding temperature is 210 ℃; wherein the mass ratio of the unidirectional PAN carbon fiber PVB prefabricated film to the high-temperature telomerized polycyclic aromatic hydrocarbon mixture is 1.6.
And 4, performing high-temperature carbonization treatment on the carbon-carbon composite bipolar plate precursor to prepare the all-carbon-carbon composite bipolar plate.
The carbon-carbon composite bipolar plate precursor was carbonized, heated in a tube furnace, supported with pure nickel foil, and heated to a high carbonization temperature with argon as a carrier gas (the carbonization process parameters are listed in table 4). The flow of argon in the high-temperature carbonization treatment process is 260ml/min, so that the carbon-carbon composite material bipolar plate is prepared.
TABLE 4 influence of carbonization Process parameters of carbon-carbon composite Bipolar plate precursors on Bipolar plate Performance
Figure BDA0002989173770000181
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (10)

1. The preparation method of the carbon-carbon composite bipolar plate is characterized by comprising the following steps:
step 1, preparing a unidirectional PAN carbon fiber prefabricated film by using polyacrylonitrile carbon fibers and polyvinyl butyral;
step 2, performing solvent extraction and grading treatment on the coal tar pitch by using a toluene-benzyl alcohol mixed solvent to obtain a polycyclic aromatic hydrocarbon mixture; carrying out high-temperature telomerization polymerization on the fused ring aromatic hydrocarbon mixture in the presence of elemental iodine to prepare a fused ring aromatic hydrocarbon polycondensate;
the mass ratio of the toluene-benzyl alcohol mixed solvent to the coal tar pitch is 3: 1-6: 1;
the volume ratio of toluene to benzyl alcohol in the toluene-benzyl alcohol mixed solvent is 1: 1-4: 1;
step 3, arranging the unidirectional PAN carbon fiber prefabricated film prepared in the step 1 according to the orientation of 0-90 ° - +45 ° - -45 ° - +45 ° -90 ° -0 °, and performing hot-press molding on the arranged unidirectional PAN carbon fiber prefabricated film and the condensed ring aromatic hydrocarbon polycondensate prepared in the step 2 to prepare a carbon-carbon composite bipolar plate precursor;
and 4, performing high-temperature carbonization treatment on the carbon-carbon composite bipolar plate precursor to prepare the all-carbon-carbon composite bipolar plate.
2. The method for preparing the carbon-carbon composite bipolar plate according to claim 1, wherein in the step 1, polyacrylonitrile carbon fibers are heated in air at 350-450 ℃ for 10-50 min;
and (3) soaking the polyacrylonitrile carbon fiber subjected to heating treatment in a polyvinyl butyral ethanol solution with the mass concentration of 0.4-4%, arranging the polyacrylonitrile carbon fiber on a polytetrafluoroethylene substrate, and preparing the unidirectional PAN carbon fiber prefabricated film after ethanol is completely volatilized.
3. The method for preparing the carbon-carbon composite bipolar plate according to claim 2, wherein in the step 1, the polyacrylonitrile carbon fiber has a length of 5.0 to 50 mm;
the surface density of the unidirectional PAN carbon fiber prefabricated film is 5.0-50 mg/cm2。
4. The method for preparing a carbon-carbon composite bipolar plate according to claim 1, wherein in the step 2, the temperature of the solvent extraction and classification treatment is 40 to 90 ℃, the treatment time is 30 to 180min, and the mechanical stirring speed adopted in the treatment process is 90 to 300 r/min; and after the solvent extraction and classification treatment is finished, separating the solvent by adopting reduced pressure distillation to obtain a polycyclic aromatic hydrocarbon mixture.
5. The method for preparing a carbon-carbon composite bipolar plate according to claim 1, wherein in the step 2, the high temperature telomerization polymerization temperature is 120 to 350 ℃, and the high temperature telomerization polymerization time is 0.5 to 4.5 hours;
the molar ratio of iodine elements in the elemental iodine to carbon elements in the fused ring aromatic hydrocarbon mixture is 0.005-0.045.
6. The method of manufacturing a carbon-carbon composite bipolar plate according to claim 1, wherein in the step 2, in the fused ring aromatic hydrocarbon mixture, the number of carbons of the average total molecular aromatic rings is 24.2 to 29.0, and the total number of the average molecular aromatic rings is 6.0 to 7.8.
7. The method for producing a carbon-carbon composite bipolar plate according to claim 1, wherein in the step 3, the condensed ring aromatic condensation polymer is provided above the unidirectional PAN carbon fiber preform film during hot press forming; the hot press molding temperature is 150-260 ℃;
the mass ratio of the unidirectional PAN carbon fiber prefabricated film to the condensed ring aromatic condensation polymer is 0.2-3.0.
8. The method for preparing a carbon-carbon composite bipolar plate according to claim 1, wherein in the step 4, the temperature rise rate of the high-temperature carbonization treatment is 1.0 to 10 ℃/min, the carbonization treatment temperature is 850 to 1200 ℃, and the carbonization treatment time is 0.6 to 6.0 hours;
the flow of argon in the high-temperature carbonization treatment process is 50-700 ml/min.
9. A carbon-carbon composite bipolar plate, which is prepared by the method for preparing the carbon-carbon composite bipolar plate according to any one of claims 1 to 8;
the preparation raw materials of the carbon-carbon composite bipolar plate comprise polyacrylonitrile carbon fiber, polyvinyl butyral, coal tar pitch, a toluene-benzyl alcohol mixed solvent and elemental iodine;
the mass ratio of the toluene-benzyl alcohol mixed solvent to the coal tar pitch is 3: 1-6: 1;
the volume ratio of toluene to benzyl alcohol in the toluene-benzyl alcohol mixed solvent is 1: 1-4: 1.
10. A PEM fuel cell comprising the carbon-carbon composite bipolar plate of claim 9; or, a carbon-carbon composite bipolar plate produced by the method for producing a carbon-carbon composite bipolar plate according to any one of claims 1 to 8.
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