CN112663189A - Mixed yarn and manufacturing method thereof, carbon paper and manufacturing method thereof - Google Patents
Mixed yarn and manufacturing method thereof, carbon paper and manufacturing method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation methods of porous conductive materials, and particularly relates to a mixed yarn and a manufacturing method thereof, and carbon paper and a manufacturing method thereof. The mixed yarn and the manufacturing method thereof can solve the problem of uneven distribution of resin and fiber, and the carbon paper prepared from the mixed yarn can solve the problems of uneven flow distribution of a binder in the carbon paper and loss of the binder among short carbon fibers in a carbonization process, thereby improving the conductivity of the carbon paper. The preparation method comprises the following steps: putting the mixture of the chopped carbon fibers, the thermoplastic resin fibers, the Novolak type phenolic resin particles and the curing agent particles into water, pulping to uniformly disperse the carbonized fiber filaments to form a suspension, and mixing and papermaking to form mixed yarns; melting phenolic resin to coat the surfaces of the carbon fibers and the thermoplastic resin fibers by a heating coating process; and then, carrying out a heating and pressurizing process at the temperature above the glass transition temperature of the thermoplastic resin fibers to ensure that the resin flows fully and uniformly and is carbonized to obtain the conductive carbon paper.
Description
Technical Field
The invention belongs to the technical field of preparation methods of porous conductive materials, and particularly relates to a mixed yarn and a preparation method thereof, conductive carbon paper prepared from the mixed yarn and a preparation method thereof.
Background
The carbon paper for proton exchange membrane hydrogen fuel cell is a porous electrode base material which is composed of chopped carbon fibers which are randomly interlaced, the chopped carbon fibers are bonded by a polymer adhesive, and the polymer adhesive is converted into a carbon material through carbonization. The carbon paper has the functions of current collection, gas transmission, airflow distribution, generated water discharge and the like.
The Chinese invention patent CN111549573A discloses a preparation method of carbon paper for proton exchange membrane hydrogen fuel cells, wherein the binder is phenolic resin, polyacrylonitrile resin with the hydrolysis degree of 10-90%, chitosan resin, furan resin and the like, and the solvent is water, methanol or ethanol. However, since the polymer binder has poor flowability at high temperature, the polymer binder between the chopped carbon fibers is easily lost by pyrolysis, and the carbon structure converted from the binder molecules after carbonization is reduced, so that it is difficult to significantly improve the conductivity of the carbon paper.
Disclosure of Invention
The invention provides a mixed yarn and a manufacturing method thereof, carbon paper and a manufacturing method thereof, and mainly aims to introduce thermoplastic resin into carbon fiber paper and coat phenolic resin on the surfaces of carbon fiber and the thermoplastic resin, so that the phenolic resin has enough fluidity along with the thermoplastic resin at high temperature, the problem of binder loss among chopped carbon fibers in a carbonization process can be solved, and the conductivity of the carbon paper can be effectively improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hybrid yarn is a porous yarn composed of chopped carbon fibers, thermoplastic resin fibers, Novolak-type phenolic resin particles and curing agent particles.
The chopped carbon fibers are not particularly limited, and may be polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, regenerated cellulose-based carbon fibers, phenol resin-based carbon fibers, or the like.
Further, the thermoplastic resin fiber is one or a combination of two or more of polyethylene fiber, polypropylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polystyrene fiber, polyamide fiber, and polycarbonate fiber.
Further, in the present invention,the surface density of the mixed yarn is 5-50 g/m2. If the areal density is less than 5g/m2The forming of the mixed yarn is difficult, and the mechanical strength is obviously reduced; if the areal density is higher than 50g/m2The pores are too dense, the air permeability is reduced, and the resin wettability is deteriorated in the hot coating stage.
Further, the thickness of the mixed yarn is 0.02-0.8 mm. If the thickness is less than 0.02mm, the mechanical property is poor and the support is not enough; if the thickness is more than 0.8mm, wettability in the thickness direction is deteriorated, and properties such as conductivity of the carbon paper at a later stage are caused.
Further, the mass ratio of the chopped carbon fibers, the thermoplastic resin fibers, the Novolak type phenolic resin particles and the curing agent particles is 1: 0.6-1.2: 0.2-0.8: 0.01 to 0.1; if the using amount of the thermoplastic resin fibers is too small, the thermoplastic resin fibers are not enough to ensure sufficient flow among the carbon fibers in the later period, and the phenolic resin is distributed on the surfaces of the carbon fibers; if the amount of the thermoplastic resin fiber is too much, the carbon residue rate after carbonization treatment is low, the mutual bonding between fibers is weak, and the mechanical property is reduced. If the dosage of the Novolak type phenolic resin particles is too small, a uniform coating cannot be formed on the surfaces of the carbon fibers and the thermoplastic resin fibers, and the wettability and the distribution uniformity of the carbon fibers and the thermoplastic resin fibers cannot be improved; if the amount of the Novolak type phenol resin particles is too large, the carbon content of the resin becomes too high and the gas permeability becomes poor.
Further, the length of the chopped carbon fiber is 1-30 mm. If the length of the chopped carbon fibers is less than 1mm, the mechanical properties of the mixed yarn and the final carbon paper are deteriorated; if the length of the chopped carbon fibers is more than 30mm, the chopped carbon fibers are difficult to disperse in water, and it is difficult to prepare a uniform paper body.
Further, the diameter of the chopped carbon fiber is 2-20 μm. If the diameter of the chopped carbon fiber is less than 2 μm, the energy consumption in the production process is increased, and the preparation cost of the carbon paper is too high; if the diameter of the chopped carbon fibers exceeds 20 μm, it will result in deterioration of mechanical properties of the carbon paper.
Further, the thermoplastic resin fibers have an average length of 1 to 30 mm. If the length of the thermoplastic resin fiber is less than 1mm, it will result in deterioration of mechanical properties of the mixed yarn and the final carbon paper; if the length of the thermoplastic resin fiber is more than 30mm, it will be difficult to disperse the thermoplastic resin fiber in water, and it will be difficult to prepare a uniform sheet.
Further, the thermoplastic resin fibers have an average diameter of 1 to 50 μm. If the diameter of the thermoplastic resin fiber is less than 1 μm, it will result in increased energy consumption during the production process and excessive manufacturing cost; if the diameter of the thermoplastic resin fiber exceeds 50 μm, it is not matched with the diameter of the carbon fiber, resulting in failure of uniform dispersion and papermaking and poor subsequent structural properties.
Further, the Novolak-type phenol resin particles have an average particle diameter of 10 to 200 μm. If the average particle size of the Novolak type phenolic resin particles is less than 10 mu m, the Novolak type phenolic resin particles are easy to run off in the papermaking process or delaminate from a fiber main body, so that the quality of mixed yarns is poor; if the average particle diameter of the Novolak type phenol resin particles is larger than 200. mu.m, the particle size is also greatly different from the fiber diameter, and a uniform mixed yarn cannot be formed.
Further, the average particle diameter of the curing agent particles is 10 to 200 μm. If the particle size of the curing agent is too small or too large, uniform papermaking with the fibers is not facilitated.
A method of making a hybrid yarn comprising the steps of: the composite material is prepared by uniformly dispersing chopped carbon fibers, thermoplastic resin fibers, Novolak type phenolic resin particles and curing agent particles in water and performing a papermaking process.
The chopped carbon fibers are not particularly limited, and may be polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, regenerated cellulose-based carbon fibers, phenol resin-based carbon fibers, or the like.
Further, the thermoplastic resin fiber is one or a combination of two or more of polyethylene fiber, polypropylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polystyrene fiber, polyamide fiber, and polycarbonate fiber.
Further, the length of the chopped carbon fiber is 1-30 mm. If the length of the chopped carbon fibers is less than 1mm, the mechanical properties of the mixed yarn and the final carbon paper are deteriorated; if the length of the chopped carbon fibers is more than 30mm, the chopped carbon fibers are difficult to disperse in water, and it is difficult to prepare a uniform paper body.
Further, the diameter of the chopped carbon fiber is 2-20 μm. If the diameter of the chopped carbon fiber is less than 2 μm, the energy consumption in the production process is increased, and the preparation cost of the carbon paper is too high; if the diameter of the chopped carbon fibers exceeds 20 μm, it will result in deterioration of mechanical properties of the carbon paper.
Further, the concentration of the chopped carbon fibers in water is 0.01 wt% to 0.5 wt%. If the concentration of the chopped carbon fibers in water is lower than 0.01 wt%, a large amount of water is used in the preparation process, water resources are wasted, and the requirement on equipment is higher; if the concentration of the chopped carbon fibers in water is higher than 0.5 wt%, the carbon fibers are easily bunched or agglomerated and are difficult to uniformly disperse, so that the quality of the prepared mixed yarn is poor.
Further, the thermoplastic resin fibers have an average length of 1 to 30 mm. If the length of the thermoplastic resin fiber is less than 1mm, it will result in deterioration of mechanical properties of the mixed yarn and the final carbon paper; if the length of the thermoplastic resin fiber is more than 30mm, it will be difficult to disperse the thermoplastic resin fiber in water, and it will be difficult to prepare a uniform sheet.
Further, the thermoplastic resin fibers have an average diameter of 1 to 50 μm. If the average diameter of the thermoplastic resin fibers is less than 1 μm, it will result in an additional increase in energy consumption during the production process, resulting in a significant increase in the production cost of the carbon paper; if the average diameter of the thermoplastic resin fibers is more than 50 μm, the flowability during carbonization becomes too high, the structure of the carbon paper becomes non-uniform, and the power generation efficiency of the carbon paper is reduced.
Further, the concentration of the thermoplastic resin fiber in water is 0.01 wt% to 0.5 wt%. If the concentration of the thermoplastic resin fibers in water is less than 0.01 wt%, it does not match the amount of the carbon fibers; if the concentration of the thermoplastic resin fibers in water is higher than 0.5% by weight, the thermoplastic resin fibers are liable to agglomerate.
Further, the Novolak-type phenol resin particles have an average particle diameter of 10 to 200 μm. If the average particle size of the Novolak type phenolic resin particles is less than 10 mu m, the Novolak type phenolic resin particles are easy to run off in the papermaking process or delaminate from a fiber main body, so that the quality of mixed yarns is poor; if the average particle diameter of the Novolak type phenolic resin particles is more than 200 μm, the particle size is also greatly different from the fiber diameter, and a uniform mixed yarn cannot be formed, and in addition, the flow of the phenolic resin during the heat treatment process is not uniform, which causes the structure of the carbon paper to be non-uniform, and thus the power generation performance of the carbon paper is low.
Further, the concentration of the Novolak type phenolic resin particles in water is 0.02 wt% to 1 wt%. If the concentration of the Novolak type phenolic resin particles in water is lower than 0.02 wt%, the surfaces of the carbon fibers and the thermoplastic resin fibers cannot be uniformly coated in the later thermal coating process; if the concentration of the phenolic resin particles of Novolak type in water is higher than 1 wt%, particle agglomeration has occurred.
Further, the average particle diameter of the curing agent particles is 10 to 200 μm. The curing agent with too small or too large particle size is not favorable for uniform papermaking with the fiber. Further, if the average diameter of the curing agent particles is more than 200. mu.m, the function as a curing agent is not sufficiently exhibited, and the structure of the carbon paper is not uniform, resulting in a decrease in power generation performance.
Further, the concentration of the curing agent particles in water is 0.01 wt% to 0.2 wt%. The concentration of the curing agent particles in water is less than 0.01 wt% and is insufficient to cure the Novolak-type phenolic resin particles; the concentration of the curing agent particles in water is higher than 0.2 wt%, which causes the use amount of the curing agent as the curing agent to be excessive, and further causes the carbon paper structure to be damaged in the carbonization process, thereby causing the reduction of the power generation performance.
A carbon paper prepared from mixed yarn is a porous electrode substrate composed of carbon fiber and resin carbon, wherein the carbon residue rate of phenolic resin is not less than 45%; the resin carbon is uniformly distributed at the intersection of the carbon fibers; the cracking of the carbon paper resin is less, and the cracking rate omega of the resin carbon is not higher than 20%; the volume resistivity in the carbon paper surface is not higher than 8m omega cm; the resistivity in the thickness direction of the carbon paper is not higher than 100m omega cm.
A method of making a carbon paper from a blended yarn comprising the steps of:
step 1, heating a coating process, namely heating mixed yarns to enable Novolak type phenolic resin particles to be molten, and thermoplastic resin fibers to be not molten, and coating the Novolak type phenolic resin on the surfaces of carbon fibers and the thermoplastic resin fibers;
step 2, heating and pressurizing the technical process, namely taking the mixed yarn subjected to thermal coating, laminating the mixed yarn above the glass transition temperature of the thermoplastic resin fiber, and heating and pressurizing to obtain a paper-like object;
and 3, carbonizing the Novolak type phenolic resin in the paper-like material to obtain the porous electrode base material, namely the carbon paper.
Further, in the heating coating process in the step 1, the heating temperature is 70-180 ℃. If the heating temperature is lower than 70 ℃, the phenolic resin cannot be uniformly coated on the surfaces of the carbon fibers and the thermoplastic resin because the heating temperature does not reach the melting temperature of the phenolic resin, so that the flowability of the phenolic resin is too high in the carbonization process, the local structure of the carbon paper is obviously different, and the improvement of the power generation performance of the carbon paper is influenced; if the heating temperature is higher than 180 ℃, the phenolic resin can not flow between carbon fiber tows due to the obvious occurrence of the solidification of the phenolic resin, and further the carbon paper has an uneven structure and the power generation performance is reduced.
Further, in the process of heating the coating in the step 1, the heating time is 1min to 30 min. If the heating time is less than 1min, it is difficult to uniformly coat the phenolic resin on the surfaces of the carbon fibers and the thermoplastic resin fibers; if the heating time is more than 30min, the production efficiency is low.
Further, in the heating and pressurizing process in the step 2, the temperature is 130-300 ℃. If the temperature is lower than 130 ℃, the thermoplastic resin fibers cannot flow; if the temperature is higher than 300 ℃, the carbon paper structure is not uniform due to the start of significant pyrolysis of the thermoplastic resin, and the power generation efficiency of the carbon paper is low.
Further, in the heating and pressurizing process in the step 2, the pressure is 0.5-5 MPa. If the use pressure is lower than 0.5MPa, the thermoplastic resin is not fully melted, and further the carbon paper has an uneven structure and low power generation performance; if the pressure is higher than 5MPa, the thermoplastic resin will be caused to excessively flow in a molten state, and the carbon paper produced will also be caused to have an uneven structure, resulting in a low power generation performance.
Further, in the heating and pressurizing process in the step 2, the time of the hot pressing treatment is 1min to 30 min. If the heating and pressurizing time is less than 1min, the structure of the carbon fiber paper is not uniform; if the heating and pressurizing time is more than 30min, the production efficiency is low.
Further, in the carbonization process described in step 3, the atmosphere used is an inert atmosphere, which may be nitrogen or argon.
Further, in the carbonization process in the step 3, the highest carbonization temperature is 1500-2300 ℃. If the highest carbonization temperature is lower than 1500 ℃, the phenolic resin in the carbon paper is insufficiently carbonized, so that the conductivity of the carbon paper is low; if the maximum carbonization temperature is higher than 2300 ℃, the graphitization degree of the carbon paper is too high, and the mechanical property of the carbon paper is low.
Further, in the carbonization process described in step 3, the heat treatment time is 5min to 2 hr. If the heat treatment time is less than 5min, the carbonization of the phenolic resin is insufficient; if the heat treatment time is more than 2hr, the production efficiency is deteriorated.
Compared with the prior art, the invention has the following advantages:
in the traditional carbon paper preparation process, the chopped carbon fibers are combined by directly adopting a method of macromolecular binder impregnation, and then carbonization is carried out to convert the macromolecular structure into a carbon body. However, in this method, since the polymer binder has poor fluidity during carbonization and it is difficult to compensate for the decrease in adhesion due to the pyrolysis of the binder between carbon fibers, the carbon paper finally formed has a small amount of carbon bodies between the chopped carbon fibers, is easily cracked, and has low electrical conductivity and low power generation efficiency.
In the new method, the thermoplastic resin fiber is added into the papermaking body, and the Novolak type phenolic resin coating with the thermoplastic property is transferred to the surfaces of the thermoplastic resin and the carbon fiber through a heating coating process, so that the Novolak type phenolic resin can be effectively transferred between the chopped carbon fibers because the thermoplastic resin fiber has melt fluidity in the carbonization process, and a carbon structure for well combining the chopped carbon fibers can be formed after carbonization, so that the prepared carbon paper has good conductivity and high power generation performance. The method avoids the problems of poor fluidity and uneven distribution caused by directly using the phenolic resin.
Detailed Description
Specific examples of the present invention are given below to further explain the constitution of the present invention. The physical properties and the like in the examples were measured by the following methods.
(1) Thickness of
The thickness of the porous electrode substrate was measured using a thickness measuring apparatus. The diameter of the columnar terminal was measured to be 10mm, and the measurement pressure was 1.5 kPa.
(2) Specific resistivity in the thickness direction
The specific resistance in the thickness direction of the porous electrode substrate was measured by sandwiching the sample between gold-plated copper plates, applying a pressure of 1MPa from above and below the gold-plated copper plates, and controlling the specific resistance at 10mA/cm2The resistance value was measured when a current was applied to the current density of (1) and was obtained by the following equation.
Specific resistivity in the thickness direction (Ω · cm) × measurement resistance value (Ω) × sample area (cm)2) Sample thickness (cm)
(3) In-plane volume resistivity
The in-plane volume resistivity of the porous electrode substrate was measured by using a four-probe resistance meter. Before measurement, the length, width and thickness of the carbon paper are measured. Calibrating a four-probe resistance tester, placing a sample on an instrument measuring table, contacting the probe with the surface, and reading the resistance. For each sample, 5 measurements were made and averaged.
(4) Average particle diameter of particles
A photograph of a sample was obtained by morphological observation using a scanning electron microscope, and the particles were analyzed for image analysis, and the average particle diameter of the particles was calculated by analyzing the outer dimensions of at least 100 particles.
(5) Cracking rate omega of resin carbon
And obtaining surface morphology observation pictures of the samples by using a scanning electron microscope, selecting areas with the area of 100 mu m by 75 mu m for carrying out crack statistics, and randomly selecting 50 areas for each sample. The cracking rate omega of the resin carbon is the proportion of the number of the areas with cracks.
Resin char cracking rate ω (number of cracked regions/50 (total observed region)
Example 1
Cutting a fiber bundle of Polyacrylonitrile (PAN) -based carbon fiber with an average fiber diameter of 7 μm to obtain polyacrylonitrile-based chopped carbon fiber with an average fiber length of 6mm for standby. Polypropylene fibers having an average fiber diameter of 10 μm were taken and cut into short fibers of 6mm for use. Taking phenolic resin particles with the average particle size of 20 mu m, and measuring the melting point to be 110 ℃ for later use. Taking hexamethylene tetramine curing agent particles with the average particle size of 10 mu m for later use.
Then, 1g of short carbon fiber, 1g of chopped polypropylene fiber, 1g of Novolak type phenolic resin particles, and 0.2g of hexamethylenetetramine curing agent particles were added to 1L of deionized water, and after sufficiently dispersing them, they were subjected to papermaking using a square papermaking machine having a papermaking surface of 300 mm. times.300 mm to obtain a sheet having a thickness of 0.10mm and an areal density of 12g/m2The hybrid yarn of (1).
The resultant mixed yarn was dried for 20 minutes by passing through a guide roll heated to 100 ℃ to sufficiently coat the surface of the carbon fiber and polyethylene fiber with Novalak type phenol resin. The carbon fiber paper is clamped in 2 pieces of release paper, the release paper is pressed for 10 minutes under the conditions of 180 ℃ and 1MPa in an intermittent hot pressing device, so that the thermoplastic resin fiber is fully melted and flows, and then the pressure is released to naturally cool to the room temperature, so that the carbon fiber paper-shaped object is obtained.
Next, the paper was heated in a batch type carbonization furnace at 1600 ℃ for 20 minutes in a nitrogen atmosphere to obtain a carbonized porous electrode substrate, that is, a carbon paper. The residual carbon rate of the phenolic resin in the obtained carbon paper is 45%, the in-plane resistivity of the carbon paper is 6.5m omega cm measured by a four-probe resistance meter, the resistivity of the carbon paper in the thickness direction is 85m omega cm measured by clamping a carbon paper sample between gold-plated copper plates, the micro-morphology of the carbon paper is observed by a scanning electron microscope, and the cracking rate omega of the resin carbon is 12%.
Examples 2 to 5
A mixed yarn was produced under the same conditions as in example 1 except that the conditions of the kind, diameter, chopped length and concentration thereof in the aqueous solution, the particle diameter and concentration of the phenol resin, the particle diameter and concentration of the curing agent, and the like of the carbon fiber were changed, and the specific conditions are shown in table 1. On the basis, the carbon paper is obtained by changing the temperature and the treatment time of the thermal coating process, the temperature, the pressure and the treatment time of the thermal pressing process and the temperature and the treatment time of the carbonization process through the thermal coating process, the thermal pressing process and the carbonization process, and the characterization of the residual carbon rate of the phenolic resin, the cracking rate of the resin carbon, the in-plane resistivity and the thickness direction resistivity is carried out on the carbon paper, and specific parameters and test results of corresponding samples are detailed in table 1.
TABLE 1
The present invention is not limited to the above embodiments, and any technical solutions similar or identical to the present invention, which are made in the light of the present invention, are within the scope of the present invention.
Claims (13)
1. The hybrid yarn is a porous yarn composed of chopped carbon fibers, thermoplastic resin fibers, Novolak-type phenolic resin particles and curing agent particles.
2. The hybrid yarn of claim 1, wherein the hybrid yarn has an areal density of 5 to 50g/m2The thickness is 0.02-0.8 mm.
3. The hybrid yarn according to claim 1, wherein the mass ratio of the chopped carbon fibers, the thermoplastic resin fibers, the Novolak-type phenolic resin particles and the curing agent particles is 1: 0.6-1.2: 0.2-0.8: 0.01 to 0.1.
4. The hybrid yarn according to claim 1, wherein the chopped carbon fibers have a length of 1 to 30mm and a diameter of 2 to 20 μm; the thermoplastic resin fibers have an average diameter of 1 to 50 μm and an average length of 1 to 30 mm; the average particle diameter of the Novolak type phenolic resin particles is 10-200 mu m; the average particle diameter of the curing agent particles is 10 to 200 μm.
5. The hybrid yarn according to claim 1, wherein the thermoplastic resin fiber is one or a combination of two or more of polyethylene fiber, polypropylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polystyrene fiber, polyamide fiber, and polycarbonate fiber.
6. A method for producing a blended yarn, characterized in that the blended yarn is produced by uniformly dispersing chopped carbon fibers, thermoplastic resin fibers, Novolak-type phenolic resin particles and curing agent particles in water and subjecting the resulting dispersion to a papermaking process.
7. The method of claim 6, wherein the chopped carbon fibers have a length of 1 to 30mm, a diameter of 2 to 20 μm, and a concentration in water of 0.01 to 0.5 wt%; the thermoplastic resin fiber has an average diameter of 1-50 μm, an average length of 1-30 mm, and a concentration of 0.01-0.5 wt% in water; the Novolak type phenolic resin particles have an average particle size of 10-200 μm and a concentration of 0.02-1 wt% in water; the average particle diameter of the curing agent particles is 10-200 mu m, and the concentration of the curing agent particles in water is 0.01-0.2 wt%.
8. The method of claim 6, wherein the thermoplastic resin fiber is one or a combination of two or more of polyethylene fiber, polypropylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polystyrene fiber, polyamide fiber, and polycarbonate fiber.
9. A carbon paper prepared from the blended yarn according to any one of claims 1 to 5, wherein the carbon paper is a porous electrode substrate composed of carbon fibers and resin char, wherein the char yield of the phenolic resin is not less than 45%, the resin char is uniformly distributed at intersections of the carbon fibers, the resin char cracks by not more than 20%, the in-plane resistivity is not more than 8m Ω -cm, and the thickness-direction resistivity is not more than 100m Ω -cm.
10. A method for manufacturing carbon paper by using the mixed yarn as claimed in any one of claims 1 to 5, wherein the carbon paper is prepared by the mixed yarn through a heating coating process, a heating and pressurizing process and a carbonization process, and the specific manufacturing process comprises the following steps:
step 1, heating a coating process, namely heating mixed yarns to enable Novolak type phenolic resin particles to be molten, and thermoplastic resin fibers to be not molten, and coating the Novolak type phenolic resin on the surfaces of carbon fibers and the thermoplastic resin fibers;
step 2, heating and pressurizing the technical process, namely heating the mixed yarn subjected to thermal coating above the glass transition temperature of the thermoplastic resin fiber, and pressurizing at the same time to obtain a paper-like object;
and 3, carbonizing the Novolak type phenolic resin in the paper-like material to obtain the porous electrode base material, namely the carbon paper.
11. The method for manufacturing carbon paper made of blended yarn according to claim 10, wherein the heating temperature used in the heating coating process of step 1 is 70-180 ℃ and the heating time used is 1-30 min.
12. The method for manufacturing carbon paper made of blended yarn according to claim 10, wherein the temperature used in the heating and pressing process in step 2 is 130 to 300 ℃, the pressure used is 0.5 to 5MPa, and the treatment time used is 1 to 30 min.
13. The method for manufacturing carbon paper from blended yarn according to claim 10, wherein the highest carbonization temperature used in the carbonization process of step 3 is 1500 to 2300 ℃ and the heat treatment time is 5min to 2 hr.
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| CN113564749A (en) * | 2021-05-31 | 2021-10-29 | 东华大学 | Preparation method of phenolic resin/modified polyvinyl alcohol composite fiber adhesive |
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