CN113871634B - Carbon fiber composite material for fuel cell bipolar plate - Google Patents
Carbon fiber composite material for fuel cell bipolar plate Download PDFInfo
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- CN113871634B CN113871634B CN202111135907.5A CN202111135907A CN113871634B CN 113871634 B CN113871634 B CN 113871634B CN 202111135907 A CN202111135907 A CN 202111135907A CN 113871634 B CN113871634 B CN 113871634B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a carbon fiber composite material for a bipolar plate of a fuel cell, which relates to the technical field of fuel cells and specifically comprises the following components: composite resin, conductive filler and modified carbon fiber. The carbon fiber surface treatment method specifically comprises the following steps: oxidizing the carbon fiber, and oxidizing the carbon fiber by adopting chromic acid solution to obtain oxidized carbon fiber; and (3) performing functional modification, namely performing chemical grafting modification on the oxidized carbon fiber by adopting 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone to obtain the modified carbon fiber. The carbon fiber composite material for the fuel cell bipolar plate has higher conductivity and bending strength and excellent conductivity and mechanical property; and the wear resistance and the wet heat resistance are obviously improved, and meanwhile, the material has good heat conduction effect.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a carbon fiber composite material for a bipolar plate of a fuel cell.
Background
A Fuel Cell (FC) is an energy conversion device capable of directly converting chemical energy into electric energy. The energy-saving type power supply has the advantages of higher energy conversion efficiency (40-60%), environmental friendliness, high starting speed, long working life and the like, and therefore, the energy-saving type power supply has been paid more and more attention, and is hopefully applied to power supplies of portable power supplies, electric automobiles, unmanned aerial vehicles, underwater submarines and the like. Currently, the main objectives of PEMFC research are to reduce system cost and improve battery performance and stability. The high cost of the fuel cell greatly constrains its commercial application and the cost of the bipolar plate accounts for 30-45% of the cost of the fuel cell stack.
The current commercial bipolar plates are mainly non-porous graphite plates and modified metal plates, wherein the non-porous graphite plates are prepared by mixing graphite and graphitizable resin and performing complex graphitization process treatment. The bipolar plate prepared by the method has low strength, needs 3-5mm thickness to keep good mechanical performance, and needs multiple times of resin impregnation in order to ensure good air tightness, and the machining process of the flow field is time-consuming and labor-consuming and has high cost. The metal plate is easy to produce in batches and has good mechanical property, but has the characteristics of poor corrosion resistance in an acid medium and larger contact resistance with a gas diffusion layer. In order to achieve higher power density, the fuel cell must effectively reduce ohmic resistance of the bipolar plate itself and contact resistance between the bipolar plate and the diffusion layer. In order to ensure that the bipolar plate is not easy to break and crush in the use process, the resin with the function of the binder is high in content, so that the composite plate is low in conductivity, high in ohmic resistance and poor in full-cell performance.
Disclosure of Invention
The invention aims to provide a carbon fiber composite material for a fuel cell bipolar plate, which has higher conductivity and bending strength and excellent conductivity and mechanical property; and the wear resistance and the wet heat resistance are obviously improved, and meanwhile, the material has good heat conduction effect.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a surface treatment method of carbon fiber, comprising:
oxidizing the carbon fiber, and oxidizing the carbon fiber by adopting chromic acid solution to obtain oxidized carbon fiber;
and (3) performing functional modification, namely performing chemical grafting modification on the oxidized carbon fiber by adopting 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone to obtain the modified carbon fiber. The invention firstly oxidizes the carbon fiber to form more active functional groups such as hydroxyl, carboxyl and the like on the surface of the carbon fiber, then adopts 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone to chemically graft and modify the surface of the oxidized fiber, then is added into a resin material as reinforcing fiber, and the bonding strength between the two is obviously enhanced; and then the composite material with excellent comprehensive performance is prepared by compounding with conductive filler, the mechanical property is obviously improved, the bending strength is more than 50MPa, and the flexibility is excellent. The presence of the modified carbon fiber in the composite material obviously improves the conductivity of the composite material, and the conductivity is more than 200S/cm; the wear resistance of the material can be improved, and the wear rate is obviously reduced; meanwhile, the heat conduction performance of the composite material can be effectively improved, and the water resistance of the composite material is improved.
Preferably, the functionalization modification method is that hydroxyl in the 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone structure and carboxyl on the surface of the carbon oxide fiber are subjected to esterification reaction.
Further, the surface treatment method of the carbon fiber specifically comprises the following steps:
oxidizing the carbon fiber, placing the carbon fiber in a sodium hydroxide aqueous solution with the concentration of 2.5-4M for pretreatment for 20-40 min, taking out and washing until the pH value of the washing solution reaches neutrality; then placing the carbon dioxide into chromic acid solution (potassium chromate: water: concentrated sulfuric acid=1:2.8-3.2:34-40), performing oxidation reaction at room temperature for 30-60 min, taking out the carbon dioxide, washing with water until the pH value of the washing solution reaches neutrality, and drying to obtain carbon dioxide fibers;
and (3) performing functional modification, namely immersing carbon oxide fibers in a THF solution containing EDCl and DMAP, activating for 0.5-1H, adding 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one with the addition of 0.18-0.26 g/mL, reacting for 10-16H at 50-60 ℃, washing with dilute hydrochloric acid and water in sequence, and drying to obtain the modified carbon fibers.
Preferably, the molar ratio of EDCl, DMAP to 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 1 to 1.3:1 to 1.2:1, a step of; the mass ratio of the carbon oxide fiber to the 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 1:0.36 to 0.55.
A carbon fiber composite material for a fuel cell bipolar plate comprising: composite resin, conductive filler and the modified carbon fiber.
Preferably, the mass ratio of the composite resin, the conductive filler and the modified carbon fiber is 0.24-0.45: 1:0.12 to 0.3.
Preferably, the composite resin includes BMI resin and CE resin.
Preferably, the composite resin further comprises N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenylamino) -4-methoxyphenyl ] acetamide. According to the invention, N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide is added in the preparation process of the composite resin, the composite resin is modified, and the modified composite resin is compounded with other components to prepare the composite material, so that the bending strength of the composite material can be effectively enhanced, and the flexibility of the composite material is improved; the wear resistance and the heat conduction performance of the composite material can be further enhanced; the water resistance of the carbon fiber composite material is effectively enhanced, and the damp-heat resistance effect is improved.
Preferably, the conductive filler includes at least one of natural crystalline flake graphite and expanded graphite.
Preferably, the purity of the natural crystalline flake graphite is 90-99.9%, and the grain size is 100-300 meshes; the particle size of the expanded graphite is 800-2000 meshes.
Further, the preparation method of the composite resin comprises the following steps:
the molar ratio is 0.6-0.8: 1, uniformly mixing BMI and CE, heating to a transparent state at 120-150 ℃ in an oil bath to obtain a prepolymer, then adding 18-30wt% of N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide, and continuing to perform prepolymerization for 40-70 min to obtain a mixed prepolymer;
coating a thin and uniform layer of silicone oil on a clean die, and placing the die into a blast constant temperature drying oven with the temperature of 140-150 ℃ for preheating for 30-50 min; slowly pouring the mixed prepolymer, defoaming for 20-40 min, then sequentially carrying out curing reaction with the temperature gradient of 150-160 ℃/2-3 h, 200-210 ℃/2-3 h and 240-250 ℃/2-3 h, and cooling and demoulding after the completion to obtain the composite resin;
or alternatively, the first and second heat exchangers may be,
the molar ratio is 0.6-0.8: 1, uniformly mixing BMI and CE, and heating to a transparent state at 120-150 ℃ in an oil bath to obtain a mixed prepolymer; coating a thin and uniform layer of silicone oil on a clean die, and placing the die into a blast constant temperature drying oven with the temperature of 140-150 ℃ for preheating for 30-50 min; then slowly pouring the mixed prepolymer, defoaming for 20-40 min, then sequentially carrying out curing reaction with the temperature gradient of 150-160 ℃/2-3 h, 200-210 ℃/2-3 h and 240-250 ℃/2-3 h, and cooling and demoulding after the completion of the curing reaction to obtain the composite resin.
The preparation method of the carbon fiber composite material for the fuel cell bipolar plate comprises the following steps:
taking composite resin, conductive filler and crushed modified carbon fiber, ball milling for 0.8-1.5 h in a ball mill at the rotating speed of 280-350 r/min to obtain mixed powder, putting the mixed powder into a mould, and performing hot press molding to obtain the composite material.
Preferably, the hot press molding conditions are: heating to 200-320 deg.c under 6-30 MPa and maintaining for 20-100 min.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone to carry out chemical grafting modification on the surface of oxidized fiber, then the oxidized fiber is added into a resin material as reinforcing fiber, and then the reinforced fiber is compounded with conductive filler to prepare the composite material with excellent comprehensive performance, the mechanical property is obviously improved, the bending strength is more than 50MPa, and the flexibility is excellent. The presence of the modified carbon fiber in the composite material obviously improves the conductivity of the composite material, and the conductivity is more than 200S/cm; the wear resistance of the material can be improved, and the wear rate is obviously reduced; meanwhile, the heat conduction performance of the composite material can be effectively improved, and the water resistance of the composite material is improved. In addition, N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide is added in the preparation process of the composite resin to modify the composite resin, so that the bending strength of the composite material can be effectively enhanced, and the flexibility of the composite material is improved; the wear resistance and the heat conduction performance of the composite material can be further enhanced; the water resistance of the carbon fiber composite material is effectively enhanced, and the damp-heat resistance effect is improved.
Therefore, the invention provides the carbon fiber composite material for the fuel cell bipolar plate, which has higher conductivity and bending strength and excellent conductivity and mechanical property; and the wear resistance and the wet heat resistance are obviously improved, and meanwhile, the material has good heat conduction effect.
Drawings
FIG. 1 is an infrared spectrum of oxidized carbon fiber and modified carbon fiber in example 1 of the present invention;
FIG. 2 is an infrared spectrum of the composite resin of examples 1 and 5 of the present invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the specific embodiments and the attached drawings:
the natural crystalline flake graphite used in the embodiment of the invention is purchased from Qingdao Guyu graphite Co., ltd, the particle size diameter is 200 meshes, and the purity is 99.9%; the expanded graphite used was purchased from the Lingshu county n Xuan mineral processing plant.
The carbon fiber used in the embodiment of the invention is chopped carbon fiber with the size of 20-25mm, and is ordered from Yaobang friction material factories in Youzhou.
Example 1:
carbon fiber surface treatment:
oxidizing carbon fibers, placing the carbon fibers in a sodium hydroxide aqueous solution with the concentration of 3.2M for pretreatment for 25min, taking out and washing until the pH value of the washing solution reaches neutrality; then placing the carbon dioxide into chromic acid solution (potassium chromate: water: concentrated sulfuric acid=1:3.1:37), performing oxidation reaction at room temperature for 45min, taking out the carbon dioxide, washing with water until the pH value of the washing solution reaches neutrality, and drying to obtain carbon dioxide fibers;
and (3) performing functional modification, namely immersing carbon oxide fibers in a THF solution containing EDCl and DMAP, activating for 1H, adding 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one with the addition of 0.24g/mL, reacting for 14H at 54 ℃, washing with dilute hydrochloric acid and water in sequence, and drying to obtain the modified carbon fibers. Wherein, the mol ratio of EDCl, DMAP and 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone is 1.3:1.1:1, a step of; the mass ratio of the carbon oxide fiber to the 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 1:0.42.
preparation of the composite resin:
the molar ratio is 0.72:1, uniformly mixing BMI and CE, and heating to a transparent state at the temperature of 138 ℃ in an oil bath to obtain a mixed prepolymer; coating a thin and uniform layer of silicone oil on a clean die, and placing the die into a blast constant temperature drying oven at 138 ℃ for preheating for 40min; then slowly pouring the mixed prepolymer, defoaming for 30min, then sequentially carrying out curing reaction with the temperature gradient of 155 ℃/2.5h, 200 ℃/2.5h and 245 ℃/2.5h, and cooling and demoulding after the completion to obtain the composite resin.
Preparation of carbon fiber composite for fuel cell bipolar plate:
the mass ratio is 0.33:1: taking composite resin, natural crystalline flake graphite and modified carbon fiber according to the proportion of 0.21, ball milling in a ball mill for 1.2h at the rotating speed of 320r/min to obtain mixed powder, and placing the mixed powder into a die for hot press molding under the hot press molding conditions that: heating to 250deg.C under 15Mpa pressure, and maintaining for 60min to obtain the final product.
Example 2:
the carbon fiber surface treatment was different from that of example 1: 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one was added in an amount of 0.19g/mL; the mass ratio of the carbon oxide fiber to the 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 1:0.38.
the preparation of the composite resin was different from example 1: the molar ratio of BMI to CE was 0.74:1.
the preparation of carbon fiber composite for fuel cell bipolar plate is different from that of example 1: the mass ratio of the composite resin to the natural crystalline flake graphite to the modified carbon fiber is 0.25:1:0.18.
example 3:
the carbon fiber surface treatment was different from that of example 1: 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one was added in an amount of 0.23g/mL; the mass ratio of the carbon oxide fiber to the 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 1:0.51.
the preparation of the composite resin was different from example 1: the molar ratio of BMI to CE was 0.68:1.
the preparation of carbon fiber composite for fuel cell bipolar plate is different from that of example 1: the mass ratio of the composite resin to the natural crystalline flake graphite to the modified carbon fiber is 0.4:1:0.23.
example 4:
the carbon fiber surface treatment was different from that of example 1: 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one was added in an amount of 0.25g/mL; the mass ratio of the carbon oxide fiber to the 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 1:0.47.
the preparation of the composite resin was different from example 1: the molar ratio of BMI to CE was 0.61:1.
the preparation of carbon fiber composite for fuel cell bipolar plate is different from that of example 1: the mass ratio of the composite resin to the expanded graphite (particle diameter of 1200 meshes) to the modified carbon fiber is 0.39:1:0.28.
example 5:
the carbon fiber surface treatment was the same as in example 1.
Preparation of the composite resin:
the molar ratio is 0.72:1, uniformly mixing BMI and CE, heating to a transparent state at the temperature of 138 ℃ in an oil bath to obtain a prepolymer, then adding 26.5wt% of N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide, and continuously prepolymerizing for 60min to obtain a mixed prepolymer;
coating a thin and uniform layer of silicone oil on a clean die, and placing the die into a blast constant temperature drying oven at 138 ℃ for preheating for 40min; then slowly pouring the mixed prepolymer, defoaming for 30min, then sequentially carrying out curing reaction with the temperature gradient of 155 ℃/2.5h, 200 ℃/2.5h and 255 ℃/2.5h, and cooling and demoulding after the completion of the curing reaction to obtain the composite resin.
The preparation of carbon fiber composite for fuel cell bipolar plate is different from that of example 1: the composite resin was prepared in this example.
Example 6:
the preparation of the composite resin was the same as in example 5.
The preparation of carbon fiber composite for fuel cell bipolar plate is different from that of example 5: and the carbon oxide fiber is adopted to replace the modified carbon fiber.
Comparative example 1:
the preparation of the composite resin was the same as in example 1.
The preparation of carbon fiber composite for fuel cell bipolar plate is different from that of example 1: and the carbon oxide fiber is adopted to replace the modified carbon fiber.
Test example 1:
characterization by Infrared Spectroscopy (FTIR)
And testing by adopting a Fourier transform infrared spectrum analyzer, and performing infrared spectrum testing by utilizing a KBr tabletting method. Wherein the test wavenumber range is 4000～500cm -1 Resolution of 4cm -1 。
The above test was performed on the oxidized carbon fiber and the modified carbon fiber obtained in example 1, and the results are shown in fig. 1. As can be seen from the analysis of the figure, 1657cm of the infrared spectrum of the modified carbon fiber obtained in example 1 was compared with the infrared spectrum of the oxidized carbon fiber -1 The characteristic absorption peak of-C=O bond still exists nearby, which indicates that the carboxyl on the surface of the grafted carbon fiber is converted into ester group; at 1550-1450 cm -1 The absorption peak of vibration characteristics of the benzene ring framework appears in the range; at 1217cm -1 Characteristic absorption peaks of C-N bonds appear nearby; at 1025cm -1 Characteristic absorption peaks of C-O bonds appear nearby; the above results indicate that the modified carbon fiber of example 1 was successfully prepared.
The composite resins prepared in example 1 and example 5 were subjected to the above test, and the results are shown in fig. 2. As can be seen from the analysis of the figure, in comparison with the infrared spectrum of the composite resin obtained in example 1, the infrared spectrum of the modified carbon fiber obtained in example 5 is clearly 2270 cm and 2240cm -1 The characteristic absorption peak of the nearby cyanate group is substantially disappeared, indicating N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo]-5- (di-2-propenylamino) -4-methoxyphenyl]The addition of acetamide can promote the reaction to be complete; at 1603cm -1 An n=n bond characteristic absorption peak appears nearby; at 1580cm -1 、1312cm -1 Near presence of-NO 2 Characteristic absorption peaks of bonds; at 1285cm -1 Characteristic absorption peaks of C-N bonds appear nearby; at 1114cm -1 Characteristic absorption peaks of C-Cl bonds appear nearby; at 1058cm -1 Characteristic absorption peaks of C-O bonds appear nearby; the above results indicate that the composite resin of example 5 was successfully prepared.
Test example 2:
1. conductivity test
The volume resistivity ρ, conductivity σ=1/ρ of each sample was measured using an SX1934 type digital four-probe tester.
The carbon fiber composite materials prepared in comparative example 1 and examples 1 to 6 were subjected to the above test, and the results are shown in table 1:
TABLE 1 results of conductive property test
From the analysis in table 1, the conductivity of the composite material prepared in example 1 is obviously higher than that of the composite material prepared in comparative example 1, which shows that the conductivity of the composite material is obviously improved by adopting 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one to carry out chemical grafting modification on the surface of carbon fiber and then compounding the carbon fiber with resin, thereby effectively improving the conductivity of the composite material. The conductivity of the composite material prepared in example 5 is equivalent to that of example 1, and the effect of example 6 is equivalent to that of comparative example 1, which shows that the addition of N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide in the preparation process of the composite resin has no negative influence on the conductivity of the carbon fiber composite material.
2. Flexural Strength test
Processing a composite material sample into a 60 multiplied by 5 multiplied by 2mm specification, and measuring the bending strength of each sample by adopting an LWK-250 type micro-control electronic tension tester and a three-point bending method, wherein the test conditions are as follows: the span is 40mm, and the movement speed of the punch is 1.0mm/min.
The carbon fiber composite materials prepared in comparative example 1 and examples 1 to 6 were subjected to the above test, and the results are shown in table 2:
TABLE 2 flexural Strength test results
| Sample of | Flexural Strength (MPa) |
| Comparative example 1 | 41.5 |
| Example 1 | 53.4 |
| Example 2 | 51.7 |
| Example 3 | 52.9 |
| Example 4 | 54.1 |
| Example 5 | 80.6 |
| Example 6 | 68.3 |
From the analysis in Table 2, the flexural strength of the composite material prepared in example 1 is obviously higher than that of comparative example 1, which shows that the flexural strength of the composite material is obviously improved by adopting 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one to carry out chemical grafting modification on the surface of carbon fiber and then compounding the carbon fiber with resin. The bending strength of the composite material prepared in the example 5 is obviously better than that of the examples 1 and 6, and the effect of the example 6 is obviously better than that of the comparative example 1, which shows that the addition of N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide in the preparation process of the composite resin can effectively enhance the mechanical property of the carbon fiber composite material; and the reinforcing effect on the mechanical property of the composite material is better under the condition that the modified carbon fiber and N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide exist simultaneously.
3. Friction wear test
A universal friction tester was used to evaluate the frictional wear behavior of the composite material. Friction test type push-to-push friction test with a contact area of 125mm 2 Test conditions: the speed was 0.275m/s, the pressure was 100N, and the test time was 60 minutes. Before each sample measurement, the sample and the dual surface were cleaned with acetone. The wear rate was calculated using the following equation:
W s ＝△m/ρF n L
wherein Deltam is the mass lost before and after the test sample; ρ is the density of the sample; f (F) n To test load pressure; l is the length of the distance of the frictional sliding.
The carbon fiber composite materials prepared in comparative example 1 and examples 1 to 6 were subjected to the above test, and the results are shown in table 3:
TABLE 3 Friction wear test results
| Sample of | Wear rate (10) -5 mm 3 /N·m) |
| Comparative example 1 | 4.73 |
| Example 1 | 3.54 |
| Example 2 | 3.63 |
| Example 3 | 3.60 |
| Example 4 | 3.41 |
| Example 5 | 1.87 |
| Example 6 | 3.09 |
From the analysis in Table 3, the abrasion rate of the composite material prepared in example 1 is obviously lower than that of comparative example 1, which shows that the abrasion rate of the composite material is obviously reduced and the abrasion resistance of the composite material is enhanced by adopting 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one to carry out chemical grafting modification on the surface of carbon fiber and then compounding the carbon fiber with resin. The abrasion rate of the composite material prepared in the example 5 is lower than that of the example 1, and the effect of the example 6 is better than that of the comparative example 1, which shows that the addition of N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide in the preparation process of the composite resin can also effectively improve the abrasion resistance of the carbon fiber composite material. And the modified carbon fiber and N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide are simultaneously present, so that the composite material has better effect of enhancing the wear resistance.
4. Thermal conductivity testing
The heat conducting property of the sample is measured by a transient planar heat source method. The test specimen was a sheet of 60X 2 mm. The specific test method comprises the following steps: polyimide insulation probes of the Hot Disk are placed between the two test samples, the heating power applied during the test is 10mW, and the test time is 10s.
The carbon fiber composite materials prepared in comparative example 1 and examples 1 to 6 were subjected to the above test, and the results are shown in table 4:
TABLE 4 thermal conductivity test results
| Sample of | Thermal conductivity (W/mK) |
| Comparative example 1 | 1.42 |
| Example 1 | 2.57 |
| Example 2 | 2.48 |
| Example 3 | 2.52 |
| Example 4 | 2.63 |
| Example 5 | 2.71 |
| Example 6 | 1.50 |
As can be seen from the analysis in Table 4, the thermal conductivity of the composite material prepared in example 1 is higher than that of comparative example 1, which shows that the thermal conductivity of the composite material prepared in example 1 is effectively improved by adopting 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one to chemically graft and modify the surface of carbon fiber and then compounding the carbon fiber with resin. The thermal conductivity of the composite material prepared in the example 5 is higher than that of the example 1, and the effect of the example 6 is better than that of the comparative example 1, which shows that the addition of N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide in the preparation process of the composite resin can effectively enhance the thermal conductivity of the carbon fiber composite material.
5. Moisture and heat resistance test
Testing was performed according to GB/T1034-2008 standard. The mass of the sample before immersion and the mass after boiling for 48 hours were weighed separately using an analytical balance, and the water absorption of the sample was calculated according to the following formula:
W％＝(W t －W 0 )/W 0 ×100％
in which W is 0 Mg is the mass of the sample before soaking; w (W) t The mass of the sample after boiling is mg.
The carbon fiber composite materials prepared in comparative example 1 and examples 1 to 6 were subjected to the above test, and the results are shown in table 5:
TABLE 5 results of wet heat resistance test
| Sample of | Water absorption (%) |
| Comparative example 1 | 1.74 |
| Example 1 | 1.63 |
| Example 2 | 1.70 |
| Example 3 | 1.65 |
| Example 4 | 1.56 |
| Example 5 | 0.82 |
| Example 6 | 0.91 |
From the analysis in Table 5, the water absorption rate of the composite material prepared in example 1 is not significantly different from that of comparative example 1, which shows that the chemical grafting modification is carried out on the surface of the carbon fiber by adopting 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone, and then the composite material is obtained by compounding the composite material with resin, so that the wet heat resistance of the carbon fiber composite material is not negatively influenced. The water absorption rate of the composite material prepared in the example 5 is lower than that of the example 1, and the effect of the example 6 is obviously better than that of the comparative example 1, which shows that the addition of N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide in the preparation process of the composite resin can effectively enhance the water resistance of the carbon fiber composite material, and the damp-heat resistance effect is improved.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. A carbon fiber composite material for a fuel cell bipolar plate comprising: composite resin, conductive filler and modified carbon fiber; the mass ratio of the composite resin to the conductive filler to the modified carbon fiber is 0.24-0.45: 1: 0.12-0.3;
the preparation method of the modified carbon fiber comprises the following steps:
oxidizing the carbon fiber, and oxidizing the carbon fiber by adopting chromic acid solution to obtain oxidized carbon fiber;
performing functional modification, namely performing chemical grafting modification on the carbon oxide fiber by adopting 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone to obtain modified carbon fiber;
the functional modification method is that hydroxyl in a 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone structure and carboxyl on the surface of carbon oxide fiber are subjected to esterification reaction.
2. The carbon fiber composite material for a fuel cell bipolar plate of claim 1, wherein: the composite resin comprises BMI resin and CE resin.
3. The carbon fiber composite material for a fuel cell bipolar plate of claim 1, wherein: the composite resin also comprises N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide.
4. The carbon fiber composite material for a fuel cell bipolar plate of claim 1, wherein: the conductive filler comprises at least one of natural crystalline flake graphite and expanded graphite.
5. The carbon fiber composite material for a fuel cell bipolar plate of claim 4, wherein: the purity of the natural crystalline flake graphite is 90-99.9%, and the particle size is 100-300 meshes; the particle size of the expanded graphite is 800-2000 meshes.
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| US7365121B2 (en) * | 2003-02-19 | 2008-04-29 | Virginia Tech Intellectual Properties, Inc. | Highly conductive thermoplastic composites for rapid production of fuel cell bipolar plates |
| US20070154771A1 (en) * | 2006-01-04 | 2007-07-05 | Jang Bor Z | Highly conductive composites for fuel cell flow field plates and bipolar plates |
| US9379393B2 (en) * | 2006-12-26 | 2016-06-28 | Nanotek Instruments, Inc. | Carbon cladded composite flow field plate, bipolar plate and fuel cell |
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