CN113871634A - 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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- CN113871634A CN113871634A CN202111135907.5A CN202111135907A CN113871634A CN 113871634 A CN113871634 A CN 113871634A CN 202111135907 A CN202111135907 A CN 202111135907A CN 113871634 A CN113871634 A CN 113871634A
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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
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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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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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, namely oxidizing the carbon fiber by using a 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 prepared by the invention has higher conductivity and bending strength, and excellent conductivity and mechanical property; and the wear resistance and the humidity resistance are obviously improved, and the material has a 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 electrical energy. The power supply has the advantages of high energy conversion efficiency (40-60%), environmental friendliness, high starting speed, long service life and the like, is concerned more and more widely, and is hopefully applied to power supplies of portable power supplies, electric automobiles, unmanned aerial vehicles, underwater vehicles and the like. Currently, the main goals of PEMFC research are to reduce system cost and improve cell performance and stability. However, the high cost of the fuel cell greatly restricts the commercial application of the fuel cell, 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, and the non-porous graphite plates are obtained by mixing graphite and graphitizable resin and performing complex graphitization process treatment. The bipolar plate prepared by the method has low strength, needs the thickness of 3-5mm to keep good mechanical property, and in addition, in order to ensure good air tightness, the graphite plate needs to be impregnated with resin for many times, and the machining process of a flow field is time-consuming, labor-consuming and high in cost. The metal plate is easy to produce in batches, has good mechanical property, but has the characteristics of poor corrosion resistance in an acid medium and large contact resistance with a gas diffusion layer. In order to achieve a higher power density, the fuel cell must effectively reduce the ohmic resistance of the bipolar plate itself and the contact resistance with the diffusion layer. In order to ensure that the bipolar plate is not easy to break and break in the using process, the resin playing the role of a binder is higher in content, so that the composite plate is lower in conductivity, large in ohmic resistance and poor in full battery 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 humidity resistance are obviously improved, and the material has a good heat conduction effect.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a surface treatment method of a carbon fiber, comprising:
oxidizing the carbon fiber, namely oxidizing the carbon fiber by using a 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 method comprises the steps of oxidizing carbon fibers to form more active functional groups such as hydroxyl, carboxyl and the like on the surfaces of the carbon fibers, carrying out chemical grafting modification on the surfaces of the oxidized fibers by adopting 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone, adding the modified oxidized fibers into a resin material as reinforcing fibers, and obviously enhancing the bonding strength between the carbon fibers and the resin material; then the composite material 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 existence 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 conductivity of the composite material can be effectively improved, and the water resistance of the composite material can be improved.
Preferably, the functionalization modification method is that hydroxyl in the structure of 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-ketone and carboxyl on the surface of the oxidized carbon fiber are subjected to esterification reaction.
Further, the surface treatment method of the carbon fiber specifically comprises the following steps:
oxidizing carbon fibers, namely putting the carbon fibers into a sodium hydroxide aqueous solution with the concentration of 2.5-4M for pretreatment for 20-40 min, taking out the carbon fibers, and washing the carbon fibers with water until the pH value of a washing solution is neutral; then placing the carbon fiber into chromic acid solution (potassium chromate, water and concentrated sulfuric acid are 1: 2.8-3.2: 34-40), carrying out oxidation reaction at room temperature for 30-60 min, taking out, washing with water until the pH value of washing liquid is neutral, and drying to obtain oxidized carbon fiber;
and (2) performing functional modification, namely soaking the oxidized carbon fiber in a THF (tetrahydrofuran) solution containing EDCl and DMAP (dimethyl acetamide) for 0.5-1H, activating, adding 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-one in an amount of 0.18-0.26 g/mL, reacting at 50-60 ℃ for 10-16H, sequentially washing with dilute hydrochloric acid and water, and drying to obtain the modified carbon fiber.
Preferably, the molar ratio of EDCl, DMAP and 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 1-1.3: 1-1.2: 1; the mass ratio of the oxidized carbon 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 for a fuel cell bipolar plate comprising: composite resin, conductive filler and the modified carbon fiber.
Preferably, the mass ratio of the composite resin to the conductive filler to the modified carbon fiber is 0.24-0.45: 1: 0.12 to 0.3.
Preferably, the composite resin comprises BMI resin and CE resin.
Preferably, the composite resin also comprises N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -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 and heat resistant effect is improved.
Preferably, the conductive filler includes at least one of natural flake graphite and expanded graphite.
Preferably, 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.
Further, a method for preparing the composite resin comprises the following steps:
the molar ratio of the components is 0.6-0.8: 1, uniformly mixing BMI and CE, heating to a transparent state in an oil bath at 120-150 ℃ to obtain a prepolymer, adding 18-30 wt% of N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide, and continuously prepolymerizing for 40-70 min to obtain a mixed prepolymer;
coating a layer of thin and uniform silicone oil on a clean mould, and putting the silicon oil into a blowing constant-temperature drying oven at the temperature of 140-150 ℃ for preheating for 30-50 min; slowly pouring the mixed prepolymer, defoaming for 20-40 min, 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, cooling and demoulding after the reaction is finished, and obtaining the composite resin;
or the like, or, alternatively,
the molar ratio of the components is 0.6-0.8: 1, uniformly mixing BMI and CE, and heating to a transparent state in an oil bath at 120-150 ℃ to obtain a mixed prepolymer; coating a layer of thin and uniform silicone oil on a clean mould, and putting the silicon oil into a blowing constant-temperature drying oven at the temperature of 140-150 ℃ for preheating for 30-50 min; and slowly pouring the mixed prepolymer, defoaming for 20-40 min, 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, cooling and demoulding after the reaction is finished, and thus obtaining the composite resin.
The preparation method of the carbon fiber composite material for the fuel cell bipolar plate comprises the following steps:
taking the composite resin, the conductive filler and the crushed modified carbon fibers, 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 die, and carrying out hot press molding to obtain the composite material.
Preferably, the hot press molding conditions are as follows: heating to 200-320 ℃ under the pressure of 6-30 Mpa, and preserving heat 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 used as a reinforcing fiber to be added into a resin material, and the resin material is compounded with a conductive filler to prepare the composite material with excellent comprehensive performance, wherein the mechanical property of the composite material is obviously improved, the bending strength is more than 50MPa, and the flexibility is excellent. The existence 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 conductivity of the composite material can be effectively improved, and the water resistance of the composite material can be 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 and heat resistant 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 humidity resistance are obviously improved, and the material has a good heat conduction effect.
Drawings
FIG. 1 is an infrared spectrum of oxidized carbon fibers and modified carbon fibers of example 1 of the present invention;
FIG. 2 is an IR spectrum of a composite resin in examples 1 and 5 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the natural crystalline flake graphite used in the embodiment of the invention is purchased from Qingdao ancient graphite Limited, the particle size is 200 meshes, and the purity is 99.9%; the expanded graphite is obtained from the processing plant of Naxu mineral products in Lingshou county.
The carbon fiber used in the embodiment of the invention is chopped carbon fiber with the size of 20-25mm, and is ordered from Yao Bangbang friction material factories in Changzhou.
Example 1:
carbon fiber surface treatment:
oxidizing carbon fibers, namely putting the carbon fibers into a 3.2M sodium hydroxide aqueous solution for pretreatment for 25min, taking out the carbon fibers, and washing the carbon fibers with water until the pH value of a washing solution is neutral; then placing the carbon fiber into chromic acid solution (potassium chromate: water: concentrated sulfuric acid is 1: 3.1: 37), carrying out oxidation reaction for 45min at room temperature, taking out the carbon fiber, washing the carbon fiber with water until the pH value of the washing solution is neutral, and drying the carbon fiber to obtain oxidized carbon fiber;
and (2) performing functional modification, namely soaking the oxidized carbon fiber in a THF (tetrahydrofuran) solution containing EDCl and DMAP (dimethyl formamide), activating for 1H, adding 0.24g/mL of 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-one, reacting for 14H at 54 ℃, sequentially washing with dilute hydrochloric acid and water, and drying to obtain the modified carbon fiber. Wherein the molar ratio of EDCl, DMAP and 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 1.3: 1.1: 1; the mass ratio of the oxidized carbon 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 composite resin:
according to a molar ratio of 0.72: 1, uniformly mixing BMI and CE, and heating to a transparent state in an oil bath at 138 ℃ to obtain a mixed prepolymer; coating a layer of thin and uniform silicone oil on a clean mould, and preheating for 40min in a blowing constant-temperature drying oven at 138 ℃; and slowly pouring the mixed prepolymer, defoaming for 30min, sequentially carrying out curing reactions with the temperature gradient of 155 ℃/2.5h, 200 ℃/2.5h and 245 ℃/2.5h, cooling and demoulding after the curing reactions are finished, thus obtaining the composite resin.
Preparation of carbon fiber composite material for fuel cell bipolar plate:
according to the mass ratio of 0.33: 1: taking the composite resin, the natural crystalline flake graphite and the modified carbon fiber according to the proportion of 0.21, ball-milling for 1.2h in a ball mill at the rotating speed of 320r/min to obtain mixed powder, putting the mixed powder into a die for hot press molding, wherein the hot press molding conditions are as follows: heating to 250 deg.C under 15Mpa, and maintaining the temperature for 60min to obtain the composite material.
Example 2:
the carbon fiber surface treatment differs from example 1: the addition amount of 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 0.19 g/mL; the mass ratio of the oxidized carbon 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 differs from that of example 1: molar ratio of BMI and CE 0.74: 1.
the preparation of the carbon fiber composite material for a fuel cell bipolar plate differs 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 differs from example 1: the addition amount of 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 0.23 g/mL; the mass ratio of the oxidized carbon 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 differs from that of example 1: molar ratio of BMI and CE 0.68: 1.
the preparation of the carbon fiber composite material for a fuel cell bipolar plate differs 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 differs from example 1: the addition amount of 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one is 0.25 g/mL; the mass ratio of the oxidized carbon 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 differs from that of example 1: molar ratio of BMI and CE 0.61: 1.
the preparation of the carbon fiber composite material for a fuel cell bipolar plate differs from that of example 1: the mass ratio of the composite resin, the expanded graphite (particle size of 1200 meshes) and 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 composite resin:
according to a molar ratio of 0.72: 1, uniformly mixing BMI and CE, heating to a transparent state in an oil bath at 138 ℃ to obtain a prepolymer, adding 26.5 wt% 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 layer of thin and uniform silicone oil on a clean mould, and preheating for 40min in a blowing constant-temperature drying oven at 138 ℃; and slowly pouring the mixed prepolymer, defoaming for 30min, then sequentially carrying out curing reactions with the temperature gradient of 155 ℃/2.5h, 200 ℃/2.5h and 255 ℃/2.5h, cooling and demoulding after the curing reactions are finished, and thus obtaining the composite resin.
The preparation of the carbon fiber composite material for a fuel cell bipolar plate differs 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 the carbon fiber composite for a fuel cell bipolar plate differs from that of example 5: oxidized carbon fibers are used to replace modified carbon fibers.
Comparative example 1:
the preparation of the composite resin was the same as in example 1.
The preparation of the carbon fiber composite material for a fuel cell bipolar plate differs from that of example 1: oxidized carbon fibers are used to replace modified carbon fibers.
Test example 1:
infrared Spectroscopy (FTIR) characterization
And testing by a Fourier transform infrared spectrum analyzer and performing infrared spectrum testing by a KBr tabletting method. Wherein the test wave number range is 4000-500 cm-1Resolution of 4cm-1。
The above-described tests were performed on the oxidized carbon fiber and the modified carbon fiber obtained in example 1, and the results are shown in fig. 1. From the analysis in the figure, it was found that 1657cm of the infrared spectrum of the modified carbon fiber obtained in example 1 was comparable to that of the oxidized carbon fiber-1A characteristic absorption peak of-C ═ O bond still exists nearby, which indicates that carboxyl on the surface of the carbon fiber is converted into ester group after grafting; at 1550-1450 cm-1A benzene ring skeleton vibration characteristic absorption peak appears in the range; at 1217cm-1A characteristic absorption peak of C-N bond appears nearby; at 1025cm-1A characteristic absorption peak of C-O bond appears nearby; the above results indicate that the modified carbon fiber of example 1 was successfully prepared.
The above tests were carried out on the composite resins obtained in examples 1 and 5, and the results are shown in FIG. 2. As is clear from the analysis of the graph, 2270 and 2240cm are clearly seen in the IR spectrum of the modified carbon fiber obtained in example 5, as compared with the IR spectrum of the composite resin obtained in example 1-1Of nearby cyanic acid groupsThe characteristic absorption peak is basically disappeared, which shows that the 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-1N is an N bond characteristic absorption peak nearby; at 1580cm-1、1312cm-1Nearby occurrence of-NO2A characteristic absorption peak of the bond; at 1285cm-1A characteristic absorption peak of C-N bond appears nearby; at 1114cm-1A characteristic absorption peak of C-Cl bond appears nearby; at 1058cm-1A characteristic absorption peak of C-O bond appears nearby; the above results indicate that the composite resin in example 5 was successfully prepared.
Test example 2:
1. measurement of conductivity
The volume resistivity ρ of each sample was measured by an SX1934 digital four-probe tester, and the conductivity σ was 1/ρ.
The results of the above tests on the carbon fiber composite materials prepared in comparative example 1 and examples 1 to 6 are shown in table 1:
table 1 conductivity test results
As can be seen from the analysis in Table 1, the conductivity of the composite material prepared in example 1 is obviously higher than that of comparative example 1, which shows that the conductivity of the composite material is obviously improved and the conductivity of the composite material is effectively improved by adopting 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 carbon fiber and compounding the carbon fiber with resin to obtain the composite material. The conductivity of the composite material prepared in the example 5 is equivalent to that of the composite material prepared in the example 1, and the effect of the composite material prepared in the example 6 is equivalent to that of the composite material prepared in the comparative example 1, which shows that the addition of the 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. Bending strength test
Processing a composite material sample into a specification of 60 multiplied by 5 multiplied by 2mm, 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 1.0 mm/min.
The results of the above tests on the carbon fiber composite materials prepared in comparative example 1 and examples 1 to 6 are shown in table 2:
TABLE 2 flexural Strength test results
| Sample (I) | Bending 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 |
As can be seen from the analysis in Table 2, the bending strength of the composite material prepared in example 1 is obviously higher than that of comparative example 1, which shows that the composite material is prepared by chemically grafting and modifying the surface of carbon fiber by using 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridine-5-one and compounding the carbon fiber with resin, so that the bending strength of the composite material is obviously improved, and the mechanical property of the composite material is improved. The bending strength of the composite material prepared in the embodiment 5 is obviously better than that of the composite material prepared in the embodiments 1 and 6, and the effect of the embodiment 6 is obviously better than that of the composite material prepared in the comparative example 1, which shows that the mechanical property of the carbon fiber composite material can be effectively enhanced by adding N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide in the preparation process of the composite resin; and the reinforcing effect on the mechanical property of the composite material is better under the condition that the modified carbon fiber and the N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide coexist.
3. Frictional wear test
A general purpose friction tester was used to evaluate the frictional wear behavior of the composite. The friction test type was a push-type friction test with a contact area of 125mm2And testing conditions are as follows: the speed was 0.275m/s, the pressure 100N, and the test time 60 min. Before each sample measurement, the sample and the mating surface are cleaned with acetone. The wear rate is calculated by the following formula:
Ws＝△m/ρFnL
in the formula, the delta m is the mass lost before and after the test sample; rho is the density of the sample; fnTo test load pressure; l is the distance length of the frictional sliding.
The results of the above tests on the carbon fiber composite materials prepared in comparative example 1 and examples 1 to 6 are shown in Table 3:
TABLE 3 Friction wear test results
| Sample (I) | Wear rate (10)-5mm3/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 |
As can be seen from the analysis in Table 3, the wear rate of the composite material prepared in example 1 is significantly lower than that of comparative example 1, which shows that the wear rate of the composite material is significantly reduced and the wear resistance of the composite material is enhanced by chemically grafting and modifying the surface of the carbon fiber with 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one and compounding the carbon fiber with resin to obtain the composite material. The wear rate of the composite material prepared in the embodiment 5 is lower than that of the composite material prepared in the embodiment 1, the effect of the embodiment 6 is better than that of the composite material prepared in the comparative example 1, and the abrasion resistance of the carbon fiber composite material can be effectively improved by adding N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide in the preparation process of the composite resin. And under the condition that the modified carbon fiber and the N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide coexist, the composite material has better enhancement effect on the wear resistance.
4. Test of Heat conductivity
The thermal conductivity of the sample was measured using a transient planar heat source method. The test specimens are sheets of 60X 2 mm. The specific test method comprises the following steps: a polyimide insulation probe of the Hot Disk is placed between the two test samples, the heating power applied during the test is 10mW, and the test time is 10 s.
The results of the above tests on the carbon fiber composite materials prepared in comparative example 1 and examples 1 to 6 are shown in table 4:
TABLE 4 Heat transfer Performance test results
| Sample (I) | 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 is effectively improved by chemically grafting and modifying the surface of the carbon fiber by using 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one and compounding the carbon fiber with resin. The thermal conductivity of the composite material prepared in the embodiment 5 is higher than that of the embodiment 1, the effect of the embodiment 6 is better than that of the comparative example 1, and the heat conductivity of the carbon fiber composite material can be effectively enhanced by adding N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide in the preparation process of the composite resin.
5. Resistance to Damp and Heat testing
The test was carried out according to GB/T1034-2008 standard. The mass of the sample before immersion and the mass after boiling in water for 48 hours were weighed using an analytical balance, and the water absorption of the sample was calculated according to the following formula:
W％＝(Wt－W0)/W0×100％
in the formula, W0Mg is the mass of the sample before immersion; wtThe mass of the sample after boiling in water is mg.
The results of the above tests on the carbon fiber composite materials prepared in comparative example 1 and examples 1 to 6 are shown in table 5:
TABLE 5 Damp and Heat resistance test results
| Sample (I) | 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 |
As can be seen from the analysis in Table 5, the water absorption of the composite material prepared in example 1 is not significantly different from that of comparative example 1, which shows that the composite material prepared by chemically grafting and modifying the surface of the carbon fiber by using 4- (4-hydroxyphenyl) -3-methyl-1-phenyl-1H-indeno [1,2-b ] pyrazolo [4,3-e ] pyridin-5-one and then compounding the carbon fiber with resin has no negative influence on the wet and heat resistance of the carbon fiber composite material. The water absorption rate of the composite material prepared in the embodiment 5 is lower than that of the embodiment 1, and the effect of the embodiment 6 is obviously better than that of the comparative example 1, which shows that the water resistance of the carbon fiber composite material can be effectively enhanced and the damp and heat resistant effect of the carbon fiber composite material is improved by adding the N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide in the preparation process of the composite resin.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. A surface treatment method of a carbon fiber, comprising:
oxidizing the carbon fiber, namely oxidizing the carbon fiber by using a 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.
2. A surface treatment method for carbon fiber according to claim 1, characterized in that: the functionalized 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 the oxidized carbon fiber are subjected to esterification reaction.
3. A carbon fiber composite for a fuel cell bipolar plate comprising: a composite resin, a conductive filler and the modified carbon fiber as recited in claim 1.
4. The carbon fiber composite material for a fuel cell bipolar plate according to claim 3, characterized in that: the mass ratio of the composite resin conductive filler to the modified carbon fiber is 0.24-0.45: 1: 0.12 to 0.3.
5. The carbon fiber composite material for a fuel cell bipolar plate according to claim 3, characterized in that: the composite resin comprises BMI resin and CE resin.
6. The carbon fiber composite material for a fuel cell bipolar plate according to claim 5, wherein: the composite resin also comprises N- [2- [ (2-chloro-4, 6-dinitrophenyl) azo ] -5- (di-2-propenyl amino) -4-methoxyphenyl ] acetamide.
7. The carbon fiber composite material for a fuel cell bipolar plate according to claim 3, characterized in that: the conductive filler comprises at least one of natural crystalline flake graphite and expanded graphite.
8. The carbon fiber composite material for a fuel cell bipolar plate according to claim 7, 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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| CN116694059A (en) * | 2023-05-23 | 2023-09-05 | 惠州学院 | High-conductivity carbon fiber composite bipolar plate base material and preparation method thereof |
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