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CN109950556B - A kind of preparation method of carbon fiber bipolar plate with three-dimensional porous structure - Google Patents

A kind of preparation method of carbon fiber bipolar plate with three-dimensional porous structure Download PDF

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CN109950556B
CN109950556B CN201910253019.XA CN201910253019A CN109950556B CN 109950556 B CN109950556 B CN 109950556B CN 201910253019 A CN201910253019 A CN 201910253019A CN 109950556 B CN109950556 B CN 109950556B
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carbon fiber
paraffin
epoxy resin
graphite felt
bipolar plate
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CN109950556A (en
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刘政
蒋百铃
罗小飞
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Xi'an Qinyuan Zhike Energy Storage Technology Co ltd
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Xian University of Technology
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Abstract

一种具有三维多孔结构的碳纤维双极板的制备方法，以聚丙烯氰基碳纤维石墨毡为导电填料和增强体材料，环氧树脂基体，石蜡为封孔剂，采用热浸渍法制备聚丙烯氰基碳纤维石墨毡/环氧树脂预浸料和聚丙烯氰基碳纤维石墨毡/石蜡预浸料；采用热压成型工艺制备含有石蜡的双极板；通过后期脱蜡工艺除掉双极板中的石蜡，最后得到双面含有碳纤维多孔结构的双极板。本发明制备工艺简单、制备成本低、环境污染小；所采用的环氧树脂基体与聚丙烯氰基碳纤维石墨毡中的碳纤维导电材料粘结力强，所制备的碳纤维双极板机械强度高，具有优异的耐电化学腐蚀性和导电性；制备过程易于控制，适用于工业化生产。

Figure 201910253019

A method for preparing a carbon fiber bipolar plate with a three-dimensional porous structure. Polyacrylonitrile carbon fiber graphite felt is used as conductive filler and reinforcement material, epoxy resin matrix, and paraffin as pore sealing agent, and polyacrylonitrile is prepared by thermal impregnation method. based carbon fiber graphite felt/epoxy resin prepreg and polyacrylonitrile carbon fiber graphite felt/paraffin prepreg; the bipolar plate containing paraffin is prepared by hot pressing process; the bipolar plate is removed by post dewaxing process. paraffin, and finally a bipolar plate containing carbon fiber porous structures on both sides is obtained. The preparation process of the invention is simple, the preparation cost is low, and the environmental pollution is small; the adopted epoxy resin matrix and the carbon fiber conductive material in the polyacrylonitrile carbon fiber graphite felt have strong adhesion, and the prepared carbon fiber bipolar plate has high mechanical strength. It has excellent electrochemical corrosion resistance and electrical conductivity; the preparation process is easy to control, and it is suitable for industrial production.

Figure 201910253019

Description

Preparation method of carbon fiber bipolar plate with three-dimensional porous structure
Technical Field
The invention belongs to the technical field of engineering material preparation, and particularly relates to a preparation method of a carbon fiber bipolar plate with a three-dimensional porous structure.
Background
In the technical field of flow battery energy storage, such as redox flow batteries including all-vanadium flow batteries, lead flow batteries and the like, the bipolar plate is one of the key components of the flow battery and provides an electrode reaction site. Due to the long-time charge and discharge state, especially under the condition of charging on the positive side of the bipolar plate, the electrochemical corrosion is serious to the bipolar plate, which can cause the performance deterioration, such as the reduction of the conductivity and the mechanical strength, and the service life of the bipolar plate is shortened. Therefore, the bipolar plate electrode material has high oxidation resistance and corrosion resistance, so that the service life of the electrode material is ensured; secondly, the bipolar plate electrode material has excellent conductivity, ohmic voltage drop in the charging and discharging process is reduced, the voltage efficiency of the battery is improved, and meanwhile, the energy loss of current in the electrode plate transmission process can be reduced, and the energy efficiency of the battery is improved; finally, the bipolar plate electrode material should have good mechanical strength to meet the strength requirements of the battery during assembly.
At present, redox flow batteries such as all-vanadium flow batteries and lead flow batteries mainly adopt conductive filler/polymer matrix composite materials, wherein the conductive filler mainly comprises carbon materials including carbon black, graphite powder, carbon fibers and the like, the polymer comprises thermoplastic resins such as polypropylene, polyethylene, polytetrafluoroethylene and the like, and thermosetting resins such as epoxy resin, phenolic resin and the like. The conductive composite material has the characteristics of light weight, easy processing, low cost and the like, and is widely adopted, and the conductivity is more than 10S/cm; the bending strength is more than 40 MPa; the electrochemical corrosion rate is less than 15 mu A/cm2. However, since the carbon material electrochemically oxidized at the positive electrode side, such as carbon black and graphite powder, is easily oxidized after long-term use, the electrochemical corrosion phenomenon is serious especially for a system with high oxidation electrode potential, and thus the service life of the battery is severely limited.
Disclosure of Invention
The invention aims to provide a carbon fiber bipolar plate with a three-dimensional porous structure, which has the characteristics of improving the conductivity and mechanical property of the existing composite material electrode plate and effectively improving the electrochemical corrosion resistance of the existing composite material electrode plate.
The invention adopts the technical scheme that the preparation method of the carbon fiber bipolar plate with the three-dimensional porous structure is implemented according to the following steps:
step 1, preparing epoxy resin glue solution and paraffin liquid;
step 2, preparing a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg by using the polypropylene cyano carbon fiber graphite felt;
step 3, preparing two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg by using two same polypropylene cyano carbon fiber graphite felts;
step 4, pressing an electrode plate with two sides containing paraffin by using a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg and two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg;
and 5, performing dewaxing treatment on the electrode plate with paraffin on two surfaces obtained in the step 4 to obtain the carbon fiber bipolar plate with a porous structure on two surfaces.
The invention is also characterized in that:
the step 1 is implemented according to the following steps:
step 1.1, mixing epoxy resin, a cross-linking agent and a catalyst, and magnetically stirring for 10-30 minutes at the temperature of 50-70 ℃ to obtain an oxygen resin glue solution;
step 1.2, liquefying the paraffin by using 110-130 ℃ silicone oil to obtain paraffin liquid.
The step 2 is implemented according to the following steps:
step 2.1, completely soaking the polypropylene cyano carbon fiber graphite felt in the epoxy resin glue solution obtained in the step 1 for 1-5 minutes;
and 2.2, after the impregnation is finished, taking out the prepreg and placing the prepreg on silicone oil paper, and then adhering a layer of silicone oil paper on the surface of the prepreg to obtain the polypropylene cyano carbon fiber graphite/epoxy resin prepreg.
Step 3 is specifically implemented according to the following steps:
step 3.1, flatly putting two same polypropylene cyano carbon fiber graphite felts into paraffin liquid, and soaking for 1-5 minutes;
and 3.2, after the impregnation is finished, taking out the prepreg and placing the prepreg on silicone oil paper, adhering a layer of silicone oil paper on the surface of the prepreg, and curing and sealing holes by paraffin at room temperature to obtain two same pieces of polypropylene cyano carbon fiber graphite felt/paraffin prepreg.
Step 4 is specifically implemented according to the following steps:
after silicone oil paper on the surfaces of the three prepregs obtained in the steps 2 and 3 is removed, sequentially putting the three prepregs into a hot-pressing die, and placing the three prepregs in the middle to be in contact stacking with the upper and lower polypropylene cyano carbon fiber graphite felt/paraffin prepreg layers without sealing one side with paraffin;
step 4.2, closing the grinding tool, then heating to 80 ℃ at the speed of 1-3 ℃/min, preserving the temperature for 180 minutes, and then gelling at the temperature of 100 ℃ and 150kgf/cm2Hot-press forming;
and 4.3, after forming, heating to 130 ℃ at the speed of 1-3 ℃/min, preserving the heat for 60-90 minutes, finally cooling to room temperature, releasing the pressure and taking out to obtain the electrode plate with paraffin on two sides.
Step 5 is specifically implemented according to the following steps:
step 5.1, placing the electrode plate with paraffin on both sides obtained in the step 4 into 120-150 ℃ silicone oil to remove the paraffin, then placing the electrode plate into 40 mass percent NaOH aqueous solution, and soaking the electrode plate for 2-3 hours at 80-90 ℃;
step 5.2, taking out the mixture after soaking, and transferring the mixture into a boiling oxalic acid solution with the mass percentage of 15% for soaking for 2-3 hours;
and 5.3, finishing soaking, and finally, sequentially carrying out ultrasonic cleaning in acetone and deionized water for 8-10 minutes to obtain the carbon fiber bipolar plate with the porous structure on both sides.
Preparing epoxy resin glue solution in the step 1, wherein the weight percentage of each component is as follows: a crosslinking agent: the catalyst is 100: 80-90: 0.1-0.3.
In the step 1, the epoxy resin is bisphenol A type and has the molecular weight of 300-700; the cross-linking agent is adipic acid; the catalyst is benzyl dimethylamine; the paraffin wax is microcrystalline wax No. 90.
The invention has the beneficial effects that:
1. the method adopts the polypropylene cyano carbon fiber graphite felt with high conductivity as the conductive material and the reinforcement material, the epoxy resin as the matrix, and the paraffin as the porous structure protective agent, so that the material source is rich and the cost is low.
2. The preparation method comprises the steps of preparing a polypropylene cyano carbon fiber graphite felt prepreg by infiltration of an epoxy resin glue solution and paraffin, preparing an electrode plate with paraffin on two sides by adopting a hot pressing process from the polypropylene cyano carbon fiber graphite felt/paraffin prepreg-polypropylene cyano carbon fiber graphite felt/resin glue solution prepreg-polypropylene cyano carbon fiber graphite felt/paraffin prepreg, wherein the intermediate compact layer (a conductive layer of the polypropylene cyano carbon fiber graphite felt/epoxy resin composite material) has high conductivity, mechanical property and electrochemical corrosion resistance.
3. The bipolar plate with the three-dimensional porous structure can be prepared by a simple dewaxing process, and the material can be used as a redox flow battery bipolar plate, and particularly a lead flow battery, can improve electrochemical corrosion resistance, improve battery efficiency and prolong the service life of the battery.
Drawings
Fig. 1 is a process flow diagram of a method for manufacturing a carbon fiber bipolar plate having a three-dimensional porous structure according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a carbon fiber bipolar plate with a three-dimensional porous structure, which is implemented according to the following steps:
step 1, preparing epoxy resin glue solution and paraffin liquid;
step 2, preparing a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg by using the polypropylene cyano carbon fiber graphite felt;
step 3, preparing two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg by using two same polypropylene cyano carbon fiber graphite felts;
step 4, pressing an electrode plate with two sides containing paraffin by using a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg and two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg;
and 5, performing dewaxing treatment on the electrode plate with paraffin on two surfaces obtained in the step 4 to obtain the carbon fiber bipolar plate with a porous structure on two surfaces.
The step 1 is implemented according to the following steps:
step 1.1, sequentially weighing and adding epoxy resin, a cross-linking agent and a catalyst into a beaker, and magnetically stirring for 10-30 minutes at the temperature of 50-70 ℃ to fully mix the epoxy resin, the cross-linking agent and the catalyst to obtain a light yellow epoxy resin glue solution;
step 1.2, weighing paraffin and pouring the paraffin into a glass groove, adding the paraffin into an oil bath kettle to 110-;
in the step 1, epoxy resin glue solution A is prepared, and the weight percentages of the components are as follows: a crosslinking agent: the catalyst is 100: 80-90: 0.1-0.3.
Wherein, the epoxy resin is bisphenol A type epoxy resin which is thermosetting resin, has good bonding strength and chemical resistance, the molecular weight is preferably 300-700, the commercial brands are E-42, E-44 and E-51, and the softening point is less than 30 ℃;
the cross-linking agent is adipic acid which is an organic dicarboxylic acid, and organic functional group carboxylic acid can be esterified with an epoxy group in the epoxy resin to generate macromolecules with a net structure;
the catalyst is benzyl dimethylamine which is organic tertiary amine and can catalyze the cross-linking agent oxalic acid to provide negative ion active center and promote the polymerization reaction of the epoxy resin and the cross-linking agent anion;
the paraffin serves as a hole sealing protector of a porous carbon fiber polypropylene cyano carbon fiber graphite felt, is No. 90 microcrystalline wax, and is characterized in that odorless and tasteless white amorphous solid wax is mainly branched saturated hydrocarbon, contains a small amount of cyclic and straight-chain hydrocarbon, has the density of about 0.9 g/mL, has the melting point of more than 90 ℃, and can retain the porous structure of the polypropylene cyano carbon fiber graphite felt through the processes of high-temperature infiltration, low-temperature curing, high-temperature dewaxing and the like;
after the mixed glue solution of the epoxy resin, the cross-linking agent and the catalyst is cured at high temperature, the elastic modulus of the mixed glue solution is more than 3GPa, and the mixed glue solution can be tightly bonded with carbon fibers in a polypropylene cyano carbon fiber graphite felt to prepare a plate with certain mechanical property, conductive function and electrochemical corrosion resistance.
The step 2 is implemented according to the following steps:
step 2.1, completely dipping the polypropylene cyano carbon fiber graphite felt into the glass containing the epoxy resin glue solution obtained in the step 1 for 1-5 minutes;
and 2.2, after the impregnation is finished, taking out the prepreg and placing the prepreg on silicone oil paper, and then attaching a layer of silicone oil paper on the surface of the prepreg to obtain the polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg.
In the step 2, the bulk density of the polypropylene cyano carbon fiber graphite felt is 0.1-0.15g/cm3Carbon content greater than 99%, polypropylene cyano carbon fiberThe conductivity of the polypropylene cyano carbon fiber in the graphite felt is more than 1 multiplied by 102S/cm. The polypropylene cyano carbon fiber graphite felt is used as a conductive filler, a three-dimensional porous structure can be provided, a large number of active points are provided for electrode reaction, and the battery efficiency is improved; meanwhile, the composite material can be used as a reinforcement to improve the bending strength of the plate; in addition, the polypropylene cyano carbon fiber has high electrochemical corrosion resistance and good chemical stability, and can improve the service life of the bipolar plate.
The resin takes a polypropylene cyano carbon fiber graphite felt as a conductive material, and the length, the width and the thickness of the polypropylene cyano carbon fiber graphite felt are 10cm, 10cm and 0.5 cm.
Step 3 is specifically implemented according to the following steps:
step 3.1, flatly placing two same polypropylene cyano carbon fiber graphite felts into the glass tank filled with paraffin liquid in the step 2, and soaking for 1-5 minutes;
and 3.2, after the impregnation is finished, taking out the prepreg and placing the prepreg on silicone oil paper, adhering a layer of silicone oil paper on the surface of the prepreg, and curing and sealing holes by paraffin at room temperature to obtain two same pieces of polypropylene cyano carbon fiber graphite felt/paraffin prepreg.
In the step 3.2, the thickness of the paraffin hole sealing is 4-5 mm.
In the step 3, the polypropylene cyano carbon fiber graphite felt is a conductive material, and the length, the width and the thickness of the polypropylene cyano carbon fiber graphite felt are 10cm, 10cm and 1 cm.
Step 4 is as shown in fig. 1, and is specifically implemented according to the following steps:
step 4.1, after silicone oil paper on the surfaces of the three prepregs obtained in the steps 2 and 3 is removed, sequentially putting the three prepregs into a hot-pressing die, and placing the three prepregs in the middle to be in contact stacking with the upper and lower polypropylene cyano carbon fiber graphite felt/paraffin prepreg on the side without sealing holes with paraffin;
step 4.2, closing the grinding tool, then heating to 80 ℃ at the speed of 1-3 ℃/min, preserving the temperature for 180 minutes, and then gelling at the temperature of 100 ℃ and 150kgf/cm2Hot-press forming;
and 4.3, after forming, heating to 130 ℃ at the speed of 1-3 ℃/min, preserving the heat for 60-90 minutes, finally cooling to room temperature along with a furnace, releasing the pressure and taking out to obtain the electrode plate with paraffin on two sides.
Step 5 is specifically implemented according to the following steps:
step 5.1, placing the electrode plate with paraffin on both sides in the step 4 into 120-150 ℃ silicon oil to remove the paraffin, then placing the electrode plate into 40 mass percent NaOH aqueous solution, and soaking the electrode plate for 2-3 hours at 80-90 ℃;
step 5.2, taking out the mixture after soaking, and transferring the mixture into a boiling oxalic acid solution with the mass percentage of 15% for soaking for 2-3 hours;
and 5.3, finishing soaking, and finally, sequentially carrying out ultrasonic cleaning in acetone and deionized water for 8-10 minutes to obtain the bipolar plate with the porous structure on both sides.
The performance test of the prepared bipolar plate needs to be explained, and according to the report of the literature, the conductivity of the polypropylene cyano carbon fiber is more than 1 x 102S/cm, the electrochemical corrosion resistance meets the requirements of the flow battery, and the performance test is mainly carried out on a middle compact layer of the bipolar plate, namely a polypropylene cyano carbon fiber graphite felt/epoxy resin conducting layer. After removing the porous polypropylene cyano carbon fiber graphite felts on the two sides of the bipolar plate, measuring the conductivity of the middle compact layer by adopting a four-probe method, wherein the conductivity is more than 1 multiplied by 102S/cm; according to the national standard GB1449-2005-T, the bending strength of the middle compact layer measured by a three-point bending method is more than 59 MPa; h at 3M2SO4Adopting an electrochemical linear polarization method as electrolyte to obtain the intermediate compact layer with the corrosion rate less than 1 muA/cm2。
Example 1
Step 1, preparing an epoxy resin solution and paraffin liquid;
step 1.1, taking epoxy resin as a matrix, and enabling the weight percentage to meet the following requirements: a crosslinking agent: sequentially weighing the epoxy resin, the cross-linking agent and the catalyst, adding the epoxy resin, the cross-linking agent and the catalyst into a beaker, and magnetically stirring the mixture for 10 minutes at the temperature of 50 ℃ to fully mix the epoxy resin, the cross-linking agent and the catalyst to obtain a light yellow epoxy resin glue solution;
step 1.2, weighing edible paraffin, pouring the edible paraffin into a glass groove, adding the edible paraffin into the glass groove by using an oil bath pan to 110 ℃, and completely liquefying the edible paraffin to obtain low-viscosity paraffin liquid with the thickness of 4 mm;
step 2, preparing a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg by using the polypropylene cyano carbon fiber graphite felt;
step 2.1, completely dipping the polypropylene cyano carbon fiber graphite felt into the glass containing the epoxy resin glue solution obtained in the step 1 for 1 minute, wherein the specification of the polypropylene cyano carbon fiber graphite felt is as follows: the dimensions of length × width × thickness are 10cm × 10cm × 0.5 cm;
and 2.2, after the impregnation is finished, taking out the prepreg and placing the prepreg on silicone oil paper, and then attaching a layer of silicone oil paper on the surface of the prepreg to obtain the polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg.
Step 3, preparing two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg by using two same polypropylene cyano carbon fiber graphite felts;
step 3.1, flatly placing two pieces of polypropylene cyano carbon fiber graphite felt which are made of the same material in the step 2 into a glass tank filled with paraffin liquid in the step 2, and soaking for 1 minute, wherein the polypropylene cyano carbon fiber graphite felt is in the specification: the dimensions of length × width × thickness are 10cm × 10cm × 1 cm;
and 3.2, after the impregnation is finished, taking out the obtained product and placing the obtained product on silicone oil paper, adhering a layer of silicone oil paper on the surface of the obtained product, and sealing holes by paraffin curing at room temperature to obtain two same pieces of polypropylene cyano carbon fiber graphite felt/paraffin prepreg, wherein the thickness of the paraffin sealed holes is 4 mm.
Step 4, pressing an electrode plate with two sides containing paraffin by using a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg and two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg;
step 4.1, after silicone oil paper on the surfaces of the three prepregs obtained in the steps 2 and 3 is removed, sequentially putting the three prepregs into a hot-pressing die, and placing the three prepregs in the middle to be in contact stacking with the upper and lower polypropylene cyano carbon fiber graphite felt/paraffin prepreg on the side without sealing holes with paraffin;
step 4.2, closing the grinding tool, and then heating to 1 DEG CHeating to 80 deg.C at a rate of/min, keeping the temperature for 120 min, and gelling at 100kgf/cm2Hot-press forming;
and 4.3, after forming, heating to 130 ℃ at the speed of 1 ℃/min, preserving the heat for 60 minutes, finally cooling to room temperature along with a furnace, releasing the pressure and taking out to obtain the electrode plate with paraffin on two sides.
Step 5, the electrode plate with double surfaces containing paraffin wax obtained in the step 4 is subjected to paraffin removal treatment to prepare a carbon fiber bipolar plate with double surfaces in a porous structure;
step 5.1, placing the electrode plate with double sides containing paraffin wax obtained in the step 4 into silicone oil at 120 ℃ to remove the paraffin wax, then placing the electrode plate into NaOH aqueous solution with the mass percentage of 40%, and soaking the electrode plate for 2 hours at 80 ℃;
step 5.2, taking out the mixture after soaking, and moving the mixture into a boiling oxalic acid solution with the mass percentage of 15% for soaking for 2 hours;
and 5.3, finishing soaking, and finally, sequentially carrying out ultrasonic cleaning in acetone and deionized water for 8 minutes to obtain the bipolar plate with the porous structure on both sides.
The performance of the prepared polypropylene cyano carbon fiber graphite felt/epoxy resin compact layer in the middle of the bipolar plate is tested, and the conductivity of the conductive plate is 2.3 multiplied by 102S/cm; the bending strength is 64 MPa; the corrosion rate is 0.2 muA/cm2。
Example 2
Step 1, preparing an epoxy resin solution and paraffin liquid;
step 1.1, taking epoxy resin as a matrix, and enabling the weight percentage to meet the following requirements: a crosslinking agent: sequentially weighing the epoxy resin, the cross-linking agent and the catalyst, adding the epoxy resin, the cross-linking agent and the catalyst into a beaker, and magnetically stirring the mixture for 14 minutes at the temperature of 54 ℃ to fully mix the epoxy resin, the cross-linking agent and the catalyst to obtain a light yellow epoxy resin glue solution;
step 1.2, weighing the edible paraffin, pouring the edible paraffin into a glass groove, adding the edible paraffin into the glass groove by using an oil bath pan to 120 ℃, and completely liquefying the edible paraffin to obtain low-viscosity paraffin liquid with the thickness of 4 mm.
Step 2, preparing a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg by using the polypropylene cyano carbon fiber graphite felt;
step 2.1, completely dipping the polypropylene cyano carbon fiber graphite felt into the glass containing the epoxy resin glue solution obtained in the step 1 for 3 minutes, wherein the specification of the polypropylene cyano carbon fiber graphite felt is as follows: the dimensions of length × width × thickness are 10cm × 10cm × 0.5 cm;
and 2.2, after the impregnation is finished, taking out the prepreg and placing the prepreg on silicone oil paper, and then attaching a layer of silicone oil paper on the surface of the prepreg to obtain the polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg.
Step 3, preparing two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg by using two same polypropylene cyano carbon fiber graphite felts;
step 3.1, flatly placing two pieces of polypropylene cyano carbon fiber graphite felt which are made of the same material in the step 2 into a glass tank filled with paraffin liquid in the step 2, and soaking for 4 minutes, wherein the polypropylene cyano carbon fiber graphite felt is in the specification: the dimensions of length × width × thickness are 10cm × 10cm × 1 cm;
and 3.2, after the impregnation is finished, taking out and placing the impregnated paper on silicone oil paper, adhering a layer of silicone oil paper on the surface, and sealing holes by paraffin curing at room temperature to obtain two same pieces of polypropylene cyano carbon fiber graphite felt/paraffin prepreg, wherein the thickness of the paraffin sealed holes is 5 mm.
Step 4, pressing an electrode plate with two sides containing paraffin by using a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg and two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg;
step 4.1, after silicone oil paper on the surfaces of the three prepregs obtained in the steps 2 and 3 is removed, sequentially putting the three prepregs into a hot-pressing die, and placing the three prepregs in the middle to be in contact stacking with the upper and lower polypropylene cyano carbon fiber graphite felt/paraffin prepreg on the side without sealing holes with paraffin;
step 4.2, closing the grinding tool, heating to 80 ℃ at the speed of 3 ℃/min, keeping the temperature for 170 minutes, and gelling at 120kgf/cm2Hot-press forming;
and 4.3, after forming, heating to 130 ℃ at the speed of 2 ℃/min, preserving the heat for 70 minutes, finally cooling to room temperature along with a furnace, releasing the pressure and taking out to obtain the electrode plate with paraffin on two sides.
Step 5, the electrode plate with double surfaces containing paraffin wax obtained in the step 4 is subjected to paraffin removal treatment to prepare a carbon fiber bipolar plate with double surfaces in a porous structure;
step 5.1, placing the electrode plate with double sides containing paraffin wax obtained in the step 4 into silicone oil at 150 ℃ to remove the paraffin wax, then placing the electrode plate into NaOH aqueous solution with the mass percentage of 40%, and soaking the electrode plate for 2 hours at 80 ℃;
step 5.2, taking out the mixture after soaking, and moving the mixture into a boiling oxalic acid solution with the mass percentage of 15% for soaking for 2 hours;
and 5.3, finishing soaking, and finally, sequentially carrying out ultrasonic cleaning in acetone and deionized water for 9 minutes to prepare the bipolar plate with the porous structure on both sides.
The performance of the prepared polypropylene cyano carbon fiber graphite felt/epoxy resin compact layer in the middle of the bipolar plate is tested, and the conductivity of the conductive plate is 1.9 multiplied by 102S/cm; the bending strength is 63 MPa; the corrosion rate is 0.44 mu A/cm2。
Example 3
Step 1, preparing an epoxy resin solution and paraffin liquid;
step 1.1, taking epoxy resin as a matrix, and enabling the weight percentage to meet the following requirements: a crosslinking agent: sequentially weighing the epoxy resin, the cross-linking agent and the catalyst into a beaker, and magnetically stirring for 20 minutes at the temperature of 60 ℃ to fully mix the epoxy resin, the cross-linking agent and the catalyst to obtain a light yellow epoxy resin glue solution, wherein the ratio of the catalyst to the cross-linking agent to the catalyst is 100: 85: 0.2;
step 1.2, weighing the edible paraffin, pouring the edible paraffin into a glass groove, adding the edible paraffin into the glass groove by using an oil bath pan to 118 ℃, and completely liquefying the edible paraffin to obtain low-viscosity paraffin liquid with the thickness of 4 mm.
Step 2, preparing a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg by using the polypropylene cyano carbon fiber graphite felt;
step 2.1, completely dipping the polypropylene cyano carbon fiber graphite felt into the glass containing the epoxy resin glue solution obtained in the step 1 for 4 minutes, wherein the specification of the polypropylene cyano carbon fiber graphite felt is as follows: the dimensions of length × width × thickness are 10cm × 10cm × 0.5 cm;
and 2.2, after the impregnation is finished, taking out the prepreg and placing the prepreg on silicone oil paper, and then attaching a layer of silicone oil paper on the surface of the prepreg to obtain the polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg.
Step 3, preparing two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg by using two same polypropylene cyano carbon fiber graphite felts;
step 3.1, flatly placing two pieces of polypropylene cyano carbon fiber graphite felt which are made of the same material in the step 2 into a glass tank filled with paraffin liquid in the step 2, and soaking for 3 minutes, wherein the polypropylene cyano carbon fiber graphite felt is in the specification: the dimensions of length × width × thickness are 10cm × 10cm × 1 cm;
and 3.2, after the impregnation is finished, taking out the obtained product and placing the obtained product on silicone oil paper, adhering a layer of silicone oil paper on the surface of the obtained product, and sealing holes by paraffin curing at room temperature to obtain two same pieces of polypropylene cyano carbon fiber graphite felt/paraffin prepreg, wherein the thickness of the paraffin sealed holes is 4.5 mm.
Step 4, pressing an electrode plate with two sides containing paraffin by using a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg and two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg;
step 4.1, after silicone oil paper on the surfaces of the three prepregs obtained in the steps 2 and 3 is removed, sequentially putting the three prepregs into a hot-pressing die, and placing the three prepregs in the middle to be in contact stacking with the upper and lower polypropylene cyano carbon fiber graphite felt/paraffin prepreg on the side without sealing holes with paraffin;
step 4.2, closing the grinding tool, then heating to 80 ℃ at the speed of 2 ℃/min, keeping the temperature for 160 minutes, and gelling at 140kgf/cm2Hot-press forming;
and 4.3, after forming, heating to 130 ℃ at the speed of 2.5 ℃/min, preserving the heat for 80 minutes, finally cooling to room temperature along with a furnace, releasing the pressure and taking out to obtain the electrode plate with paraffin on two sides.
Step 5, the electrode plate with double surfaces containing paraffin wax obtained in the step 4 is subjected to paraffin removal treatment to prepare a carbon fiber bipolar plate with double surfaces in a porous structure;
step 5.1, placing the electrode plate with double sides containing paraffin wax obtained in the step 4 into silicone oil at 140 ℃ to remove the paraffin wax, then placing the electrode plate into NaOH aqueous solution with the mass percentage of 40%, and soaking the electrode plate for 2.5 hours at 80 ℃;
step 5.2, taking out the mixture after soaking, and transferring the mixture into a boiling oxalic acid solution with the mass percentage of 15% for soaking for 2.5 hours;
and 5.3, finishing soaking, and finally, sequentially carrying out ultrasonic cleaning in acetone and deionized water for 8.5 minutes to obtain the bipolar plate with the porous structure on both sides.
The performance of the prepared polypropylene cyano carbon fiber graphite felt/epoxy resin compact layer in the middle of the bipolar plate is tested, and the conductivity of the conductive plate is 2.1 multiplied by 102S/cm; the bending strength is 66 MPa; the corrosion rate is 0.17 muA/cm2。
Example 4
Step 1, preparing an epoxy resin solution and paraffin liquid;
step 1.1, taking epoxy resin as a matrix, and enabling the weight percentage to meet the following requirements: a crosslinking agent: sequentially weighing the epoxy resin, the cross-linking agent and the catalyst, adding the epoxy resin, the cross-linking agent and the catalyst into a beaker, and magnetically stirring the mixture for 17 minutes at the temperature of 66 ℃ to fully mix the epoxy resin, the cross-linking agent and the catalyst to obtain a light yellow epoxy resin glue solution;
step 1.2, weighing edible paraffin, pouring the edible paraffin into a glass groove, adding the edible paraffin into an oil bath kettle to 127 ℃ to completely liquefy the edible paraffin to obtain low-viscosity paraffin liquid with the thickness of 4 mm;
step 2, preparing a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg by using the polypropylene cyano carbon fiber graphite felt;
step 2.1, completely dipping the polypropylene cyano carbon fiber graphite felt into the glass containing the epoxy resin glue solution obtained in the step 1 for 2 minutes, wherein the specification of the polypropylene cyano carbon fiber graphite felt is as follows: the dimensions of length × width × thickness are 10cm × 10cm × 0.5 cm;
and 2.2, after the impregnation is finished, taking out the prepreg and placing the prepreg on silicone oil paper, and then attaching a layer of silicone oil paper on the surface of the prepreg to obtain the polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg.
Step 3, preparing two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg by using two same polypropylene cyano carbon fiber graphite felts;
step 3.1, flatly placing two pieces of polypropylene cyano carbon fiber graphite felt which are made of the same material in the step 2 into a glass tank filled with paraffin liquid in the step 2, and soaking for 2 minutes, wherein the polypropylene cyano carbon fiber graphite felt is in the specification: the dimensions of length × width × thickness are 10cm × 10cm × 1 cm;
and 3.2, after the impregnation is finished, taking out the obtained product and placing the obtained product on silicone oil paper, adhering a layer of silicone oil paper on the surface of the obtained product, and sealing holes by paraffin curing at room temperature to obtain two same pieces of polypropylene cyano carbon fiber graphite felt/paraffin prepreg, wherein the thickness of the paraffin sealed holes is 4.5 mm.
Step 4, pressing an electrode plate with two sides containing paraffin by using a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg and two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg;
step 4.1, after silicone oil paper on the surfaces of the three prepregs obtained in the steps 2 and 3 is removed, sequentially putting the three prepregs into a hot-pressing die, and placing the three prepregs in the middle to be in contact stacking with the upper and lower polypropylene cyano carbon fiber graphite felt/paraffin prepreg on the side without sealing holes with paraffin;
step 4.2, closing the grinding tool, heating to 80 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 150 minutes, and gelling at 130kgf/cm2Hot-press forming;
and 4.3, after forming, heating to 130 ℃ at the speed of 3 ℃/min, preserving the heat for 75 minutes, finally cooling to room temperature along with a furnace, releasing the pressure and taking out to obtain the electrode plate with paraffin on two sides.
Step 5, the electrode plate with double surfaces containing paraffin wax obtained in the step 4 is subjected to paraffin removal treatment to prepare a carbon fiber bipolar plate with double surfaces in a porous structure;
step 5.1, placing the electrode plate with double sides containing paraffin wax obtained in the step 4 into silicone oil at 150 ℃ to remove the paraffin wax, then placing the electrode plate into NaOH aqueous solution with the mass percentage of 40%, and soaking the electrode plate for 2.5 hours at 80 ℃;
step 5.2, taking out the mixture after soaking, and transferring the mixture into a boiling oxalic acid solution with the mass percentage of 15% for soaking for 2.5 hours;
and 5.3, finishing soaking, and finally, sequentially carrying out ultrasonic cleaning in acetone and deionized water for 8.5 minutes to obtain the bipolar plate with the porous structure on both sides.
The performance of the prepared polypropylene cyano carbon fiber graphite felt/epoxy resin compact layer in the middle of the bipolar plate is tested, and the conductivity of the conductive plate is 1.6 multiplied by 102S/cm; the bending strength is 64 MPa; the corrosion rate is 0.11 muA/cm2。
Example 5
Step 1, preparing an epoxy resin solution and paraffin liquid;
step 1.1, taking epoxy resin as a matrix, and enabling the weight percentage to meet the following requirements: a crosslinking agent: sequentially weighing the epoxy resin, the cross-linking agent and the catalyst, adding the epoxy resin, the cross-linking agent and the catalyst into a beaker, and magnetically stirring the mixture for 30 minutes at the temperature of 70 ℃ to fully mix the epoxy resin, the cross-linking agent and the catalyst to obtain a light yellow epoxy resin glue solution;
step 1.2, weighing edible paraffin, pouring the edible paraffin into a glass groove, adding the edible paraffin into the glass groove by using an oil bath pan to 130 ℃, and completely liquefying the edible paraffin to obtain low-viscosity paraffin liquid with the thickness of 4 mm;
step 2, preparing a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg by using the polypropylene cyano carbon fiber graphite felt;
step 2.1, completely dipping the polypropylene cyano carbon fiber graphite felt into the glass containing the epoxy resin glue solution obtained in the step 1 for 5 minutes, wherein the specification of the polypropylene cyano carbon fiber graphite felt is as follows: the dimensions of length × width × thickness are 10cm × 10cm × 0.5 cm;
and 2.2, after the impregnation is finished, taking out the prepreg and placing the prepreg on silicone oil paper, and then attaching a layer of silicone oil paper on the surface of the prepreg to obtain the polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg.
Step 3, preparing two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg by using two same polypropylene cyano carbon fiber graphite felts;
step 3.1, flatly placing two pieces of polypropylene cyano carbon fiber graphite felt which are made of the same material in the step 2 into a glass tank filled with paraffin liquid in the step 2, and soaking for 5 minutes, wherein the polypropylene cyano carbon fiber graphite felt is in the specification: the dimensions of length × width × thickness are 10cm × 10cm × 1 cm;
and 3.2, after the impregnation is finished, taking out the obtained product and placing the obtained product on silicone oil paper, adhering a layer of silicone oil paper on the surface of the obtained product, and sealing holes by paraffin curing at room temperature to obtain two same pieces of polypropylene cyano carbon fiber graphite felt/paraffin prepreg, wherein the thickness of the paraffin sealed holes is 4.5 mm.
Step 4, pressing an electrode plate with two sides containing paraffin by using a polypropylene cyano carbon fiber graphite felt/epoxy resin prepreg and two same polypropylene cyano carbon fiber graphite felt/paraffin prepreg;
step 4.1, after silicone oil paper on the surfaces of the three prepregs obtained in the steps 2 and 3 is removed, sequentially putting the three prepregs into a hot-pressing die, and placing the three prepregs in the middle to be in contact stacking with the upper and lower polypropylene cyano carbon fiber graphite felt/paraffin prepreg on the side without sealing holes with paraffin;
step 4.2, closing the grinding tool, heating to 80 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 180 minutes, and gelling at 150kgf/cm2Hot-press forming;
and 4.3, after forming, heating to 130 ℃ at the speed of 3 ℃/min, preserving the heat for 90 minutes, finally cooling to room temperature along with a furnace, releasing the pressure and taking out to obtain the electrode plate with paraffin on two sides.
Step 5, the electrode plate with double surfaces containing paraffin wax obtained in the step 4 is subjected to paraffin removal treatment to prepare a carbon fiber bipolar plate with double surfaces in a porous structure;
step 5.1, placing the electrode plate with double sides containing paraffin wax obtained in the step 4 into silicone oil at 150 ℃ to remove the paraffin wax, then placing the electrode plate into NaOH aqueous solution with the mass percentage of 40%, and soaking the electrode plate for 3 hours at 80 ℃;
step 5.2, taking out the mixture after soaking, and moving the mixture into a boiling oxalic acid solution with the mass percentage of 15% for soaking for 3 hours;
and 5.3, finishing soaking, and finally, sequentially carrying out ultrasonic cleaning in acetone and deionized water for 10 minutes to prepare the bipolar plate with the porous structure on both sides.
For the middle polypropylene cyano carbon fiber graphite felt/ring of the prepared bipolar plateThe oxygen resin compact layer is subjected to performance test, and the conductivity of the conductive plate is 2.4 multiplied by 102S/cm; the bending strength is 61 MPa; the corrosion rate is 0.3 mu A/cm2。
Conductivity (S/cm) Flexural Strength (MPa) Corrosion Rate (. mu.A/cm 2)
Example 1 2.3×102 64 0.2
Example 2 1.9×102 63 0.44
Example 3 2.1×102 66 0.17
Example 4 1.6×102 64 0.11
Example 5 2.4×102 61 0.3
TABLE 1
As can be seen from table 1: the electric conductivity, the bending strength and the corrosion rate of the polypropylene cyano carbon fiber graphite felt/epoxy resin compact layer conductive plate of the embodiments 1 to 5 reach and are superior to the performance standard of the American energy department bipolar plate, namely, the electric conductivity is more than 100S/cm, the bending strength is more than 59MPa, and the corrosion rate is less than 1 muA/cm2。

Claims (8)

1.一种具有三维多孔结构的碳纤维双极板的制备方法，其特征在于，具体按照以下步骤实施：1. a preparation method of a carbon fiber bipolar plate with a three-dimensional porous structure, is characterized in that, specifically implements according to the following steps: 步骤1、用110-130℃硅油液化石蜡，得到石蜡液体，所述石蜡为90号微晶蜡；同时配制环氧树脂胶液；Step 1. Use 110-130°C silicone oil to liquefy paraffin to obtain paraffin liquid, and the paraffin is No. 90 microcrystalline wax; at the same time, prepare epoxy resin glue; 步骤2、用聚丙烯氰基碳纤维石墨毡制备聚丙烯氰基碳纤维石墨毡/环氧树脂预浸料；Step 2, using polyacrylonitrile carbon fiber graphite felt to prepare polyacrylonitrile carbon fiber graphite felt/epoxy resin prepreg; 步骤3、用两块相同聚丙烯氰基碳纤维石墨毡制备两块相同聚丙烯氰基碳纤维石墨毡/石蜡预浸料；Step 3, using two identical polyacrylonitrile carbon fiber graphite felts to prepare two identical polyacrylonitrile carbon fiber graphite felts/paraffin prepregs; 步骤4、用聚丙烯氰基碳纤维石墨毡/环氧树脂预浸料与两块相同聚丙烯氰基碳纤维石墨毡/石蜡预浸料压制双面含有石蜡的电极板；Step 4. Use the polyacrylonitrile carbon fiber graphite felt/epoxy resin prepreg and two identical polyacrylonitrile carbon fiber graphite felt/paraffin wax prepregs to press the electrode plate containing paraffin on both sides; 步骤5、步骤4所得双面含有石蜡的电极板除蜡处理，制得双面呈多孔结构的碳纤维双极板。In step 5 and step 4, the electrode plate containing paraffin on both sides obtained in step 4 is subjected to dewaxing treatment to obtain a carbon fiber bipolar plate with a porous structure on both sides. 2.根据权利要求1所述的一种具有三维多孔结构的碳纤维双极板的制备方法，其特征在于，所述步骤1中环氧树脂胶液的制备方法为：2. The preparation method of a carbon fiber bipolar plate with a three-dimensional porous structure according to claim 1, wherein the preparation method of the epoxy resin glue in the step 1 is: 将环氧树脂、交联剂和催化剂混合，在50℃-70℃温度下磁力搅拌10-30分钟，得到氧树脂胶液。Mix the epoxy resin, the crosslinking agent and the catalyst, and stir magnetically for 10-30 minutes at a temperature of 50°C-70°C to obtain an oxygen resin glue. 3.根据权利要求1所述的一种具有三维多孔结构的碳纤维双极板的制备方法，其特征在于，所述步骤2具体按照以下步骤实施：3. The preparation method of a carbon fiber bipolar plate with a three-dimensional porous structure according to claim 1, wherein the step 2 is specifically implemented according to the following steps: 步骤2.1、将聚丙烯氰基碳纤维石墨毡完全浸渍在步骤1所得的环氧树脂胶液，浸渍1-5分钟；Step 2.1, fully immerse the polyacrylonitrile carbon fiber graphite felt in the epoxy resin glue obtained in step 1 for 1-5 minutes; 步骤2.2、浸渍完成后，取出放在硅油纸上，表面再附着一层硅油纸，得到聚丙烯氰基碳纤维石墨/环氧树脂预浸料。Step 2.2. After the impregnation is completed, take it out and place it on the silicone oil paper, and attach another layer of silicone oil paper to the surface to obtain the polypropylene cyanocarbon fiber graphite/epoxy resin prepreg. 4.根据权利要求3所述的一种具有三维多孔结构的碳纤维双极板的制备方法，其特征在于，所述步骤3具体按照以下步骤实施：4. The preparation method of a carbon fiber bipolar plate with a three-dimensional porous structure according to claim 3, wherein the step 3 is specifically implemented according to the following steps: 步骤3.1、将两块相同聚丙烯氰基碳纤维石墨毡平整地放入到石蜡液体中，浸渍1-5分钟；Step 3.1. Put two identical polyacrylonitrile carbon fiber graphite felts into the paraffin liquid evenly, and immerse them for 1-5 minutes; 步骤3.2、浸渍完成后，取出放在硅油纸上，表面再附着一层硅油纸，室温石蜡固化封孔，得到两块相同聚丙烯氰基碳纤维石墨毡/石蜡预浸料。Step 3.2. After the impregnation is completed, take it out and place it on the silicone oil paper, attach another layer of silicone oil paper to the surface, and solidify and seal the holes with paraffin wax at room temperature to obtain two pieces of the same polypropylene cyanocarbon fiber graphite felt/paraffin wax prepreg. 5.根据权利要求4所述的一种具有三维多孔结构的碳纤维双极板的制备方法，其特征在于，所述步骤4具体按照以下步骤实施：5. The method for preparing a carbon fiber bipolar plate with a three-dimensional porous structure according to claim 4, wherein the step 4 is specifically implemented according to the following steps: 步骤4.1、去掉步骤2、3中所得三个预浸料表面的硅油纸后，把三块预浸料依次放入到热压模具中，放置在中间聚丙烯氰基碳纤维石墨毡/环氧树脂预浸料与上下层聚丙烯氰基碳纤维石墨毡/石蜡预浸料没有用石蜡封孔一侧接触叠放；Step 4.1. After removing the silicone oil paper on the surface of the three prepregs obtained in steps 2 and 3, put the three prepregs into the hot pressing mold in turn, and place them on the middle polyacrylonitrile carbon fiber graphite felt/epoxy resin. The prepreg and the upper and lower layers of polyacrylonitrile carbon fiber graphite felt/paraffin prepreg are stacked in contact with one side that is not sealed with paraffin; 步骤4.2、合上磨具，然后以1-3℃/min的速率升温到80℃，保温120-180分钟凝胶后在100-150kgf/cm2热压成型；Step 4.2, close the abrasive tool, then raise the temperature to 80°C at a rate of 1-3°C/min, hold for 120-180 minutes, and then heat-press at 100-150kgf/cm 2 to form the gel; 步骤4.3、成型后，再以1-3℃/min的速率升温到130℃且保温60-90分钟，最后冷却至室温后泄压取出，制得双面含有石蜡的电极板。Step 4.3: After forming, the temperature is raised to 130°C at a rate of 1-3°C/min and kept for 60-90 minutes, and finally cooled to room temperature, pressure relief is removed, and an electrode plate containing paraffin on both sides is obtained. 6.根据权利要求1所述的一种具有三维多孔结构的碳纤维双极板的制备方法，其特征在于，所述步骤5具体按照以下步骤实施：6. The method for preparing a carbon fiber bipolar plate with a three-dimensional porous structure according to claim 1, wherein the step 5 is specifically implemented according to the following steps: 步骤5.1、将步骤4所得的双面含有石蜡的电极板放入到120-150℃硅油中除去石蜡，然后放入到质量百分数为40%NaOH水溶液中，在80-90℃下浸泡2-3个小时；Step 5.1. Put the electrode plate containing paraffin on both sides obtained in step 4 into silicone oil at 120-150°C to remove the paraffin, and then put it into a 40% NaOH aqueous solution, soak it at 80-90°C for 2-3 Hours; 步骤5.2、浸泡结束后取出移入在沸腾的质量百分数为15%草酸溶液中浸泡2-3个小时；Step 5.2, after soaking, take out and move it into a boiling mass percentage of 15% oxalic acid solution to soak for 2-3 hours; 步骤5.3、浸泡结束，最后依次在丙酮和去离子水中超声清洗8-10分钟，制得双面呈多孔结构的碳纤维双极板。Step 5.3, the soaking is completed, and finally ultrasonic cleaning is performed in acetone and deionized water for 8-10 minutes in sequence to obtain a carbon fiber bipolar plate with a porous structure on both sides. 7.根据权利要求2所述的一种具有三维多孔结构的碳纤维双极板的制备方法，其特征在于，步骤1中环氧树脂胶液配置，要求各组分的重量百分比为环氧树脂：交联剂：催化剂＝100 : 80-90 : 0.1-0.3。7. The preparation method of a carbon fiber bipolar plate with a three-dimensional porous structure according to claim 2, wherein the epoxy resin glue liquid configuration in step 1 requires that the weight percent of each component is epoxy resin: Cross-linking agent: catalyst=100 : 80-90 : 0.1-0.3. 8.根据权利要求7所述的一种具有三维多孔结构的碳纤维双极板的制备方法，其特征在于，所述步骤1中环氧树脂为双酚A型，分子量为300-700；催化剂为苄基二甲胺。8 . The method for preparing a carbon fiber bipolar plate with a three-dimensional porous structure according to claim 7 , wherein in the step 1, the epoxy resin is bisphenol A type, and the molecular weight is 300-700; the catalyst is Benzyldimethylamine.
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