CN111883794A - Layered graphite composite bipolar plate and preparation method thereof - Google Patents

Layered graphite composite bipolar plate and preparation method thereof Download PDF

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Publication number
CN111883794A
CN111883794A CN202010734155.3A CN202010734155A CN111883794A CN 111883794 A CN111883794 A CN 111883794A CN 202010734155 A CN202010734155 A CN 202010734155A CN 111883794 A CN111883794 A CN 111883794A
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graphite
graphite composite
resin
master batch
plate
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明平文
郑俊生
张存满
彭宇航
樊润林
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Tongji University
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Tongji University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0221—Organic resins; Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a layered graphite composite bipolar plate and a preparation method thereof. Compared with the prior art, the intermediate layer is made of the thermoplastic composite material, so that the feeding precision of the thermosetting composite material is improved in the manufacturing process, and the problem of low molding reliability of the thermosetting composite material with high carbon content is solved; in addition, the middle layer with high resin content in the layered polar plate improves the bending strength and air tightness of the bipolar plate, and the surface layer with high carbon content improves the electrical conductivity of the bipolar plate; the improvement of the overall performance of the bipolar plate is realized by respectively optimizing different functional layers, and meanwhile, the preparation process is simple and convenient, is beneficial to batch production and has higher practical value.

Description

Layered graphite composite bipolar plate and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, relates to a proton exchange membrane fuel cell, and particularly relates to a layered graphite composite bipolar plate and a preparation method thereof.
Background
The fuel cell technology has wide application prospect by virtue of a clean and efficient energy conversion mechanism. In particular, Proton Exchange Membrane Fuel Cells (PEMFCs) have a fast start-up speed and a low operating temperature, and are the most suitable fuel cell type for large-scale applications. The bipolar plate is one of the key components of the fuel cell, and plays a plurality of functions of isolating and distributing cathode and anode reactants, collecting current, conducting heat, sealing, supporting a membrane electrode and the like in the fuel cell. Thus, the volume and performance of the bipolar plate has a direct impact on the performance of the fuel cell.
The bipolar plates currently applied to PEMFCs can be classified into graphite bipolar plates, metal bipolar plates, and composite bipolar plates according to the preparation material. Graphite bipolar plates have good electrical conductivity and corrosion resistance, but are relatively weak in bending strength and gas tightness, and generally require relatively thick plates to meet practical requirements. In addition, the difficulty of processing the fine flow channel structure on the surface of the bipolar plate is high, and the fine flow channel structure becomes an important factor for limiting the wide application of the graphite bipolar plate. The metal bipolar plate has obvious advantages in the aspects of conductivity, bending strength, machining performance and the like. However, the metal bipolar plate is in a high-temperature acidic environment in the PEMFC, and is prone to corrosion and dissolution, or an oxide layer is formed on the surface of the plate. The conductivity of the metal bipolar plate is reduced, and meanwhile, dissolved metal ions can be diffused into a proton exchange membrane, so that the working performance of the PEMFC is greatly influenced. The composite bipolar plate takes the polymeric material of graphite reinforced resin as a matrix, and has the basic characteristics of low price, simple and convenient preparation process, light weight, good corrosion resistance and the like. The performance of the composite bipolar plate is influenced by the content of graphite, the preparation process and the like, and has larger differences in conductivity, bending strength, process performance and the like. The current optimization thinking mainly focuses on the performance optimization of resin and the improvement of hot molding process, and the contradiction between the electrical conductivity and the bending strength is difficult to be fundamentally improved.
In order to solve the problem that the single composite material can not effectively solve the contradiction of the performance balance of the bipolar plate, Chinese patent CN107819137A of the institute of Metal in the Chinese academy of sciences discloses a flexible graphite bipolar plate and a preparation method thereof, and proposes that a metal mesh and carbon cloth are used as conductive frameworks, and are compositely coated with graphite/resin, and finally, the flexible graphite paper is laminated and molded to form the composite bipolar plate. This patent introduces the concept of a reinforcing structure to achieve an increase in the overall performance of the bipolar plate.
The Guangdong Hongyen technology limited company discloses an ultrathin flexible graphite bipolar plate and a preparation method thereof in Chinese patent CN109921051A, and provides a method for reinforcing a flexible graphite plate by using a graphene film.
Disclosure of Invention
The problems of reducing the forming thickness of the graphite composite bipolar plate and precisely forming a flow channel cannot be effectively solved in the prior art. The invention aims to provide a layered graphite composite bipolar plate and a preparation method thereof, aiming at solving the problems of reducing the forming thickness of the graphite composite bipolar plate and precisely forming a flow channel.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a layered graphite composite bipolar plate, which comprises an intermediate layer and surface layers arranged on two sides of the intermediate layer, wherein the intermediate layer is a thermoplastic resin/graphite composite material plate, the surface layers are thermosetting resin/graphite composite material layers, and the outer surfaces of the surface layers are provided with flow channel structures.
As a preferred embodiment of the present invention, the flow channel structure is formed by hot molding on the surface layer and is cured to a depth less than the thickness of the surface layer, and the intermediate layer maintains a planar structure and does not participate in the flow channel molding. The structure can effectively exert the function that the middle layer ensures the bending strength of the polar plate, can realize the aim of improving the forming precision of the flow channel structure only by optimizing the formula of the surface layer, is convenient for the formula optimization of the layered composite polar plate, and provides a solution for solving the problem that the forming performance and the service performance are difficult to be considered.
In a preferred embodiment of the present invention, the thermoplastic resin/graphite composite plate is formed by processing a composite material made of a thermoplastic resin and a graphite material.
As a further preferred embodiment of the present invention, the thermoplastic resin comprises fluorinated ethylene-propylene (FEP), and/or polypropylene (PP), and/or Polyphenylene Sulfide (PPs), and/or polyvinylidene fluoride (PVDF), and/or Polycarbonate (PC), and/or Polyoxymethylene (POM).
As a further preferred embodiment of the present invention, the graphite material comprises natural crystalline flake graphite, and/or expanded graphite, and/or carbon fiber powder, and/or chopped carbon fiber.
In a further preferred embodiment of the present invention, the mass ratio of the thermoplastic resin to the graphite material is 3:7 to 7: 3. Further preferably, the mass ratio of the thermoplastic resin to the graphite material is 5: 5.
In a further preferred embodiment of the present invention, the graphite material has a particle size of 1 μm to 200 μm, and when the graphite material contains chopped carbon fibers, the chopped carbon fibers have a length of 1mm to 5 mm. It is further preferred that the particle size of the graphite material is 40 μm to 80 μm.
In a more preferred embodiment of the present invention, the thickness of the thermoplastic resin/graphite composite plate is 0.1mm to 0.4 mm. It is further preferable that the thickness of the thermoplastic resin/graphite composite plate is 0.1mm to 0.2 mm.
As a preferred embodiment of the present invention, the thermosetting resin/graphite composite material layer is made of a master batch in which a thermosetting resin and a graphite material are mixed.
As a further preferred embodiment of the present invention, the graphite material comprises natural flake graphite, and/or expanded graphite, and/or carbon fiber, and/or graphene nanoplatelets, and/or highly conductive carbon black.
As a further preferred embodiment of the present invention, the thermosetting resin is a thermosetting resin with a lower curing temperature, including an epoxy resin (EP), and/or a phenol resin (PF), and/or a polyimide resin (PI), and/or a Vinyl Ester Resin (VER), and/or a polybenzoxazine resin (PBA), and/or a Urea Resin (UR), and/or a polyurethane resin (PU).
In a further preferred embodiment of the present invention, the mass ratio of the graphite material to the thermosetting resin is 7:3 to 9:1.
In a further preferred embodiment of the present invention, the graphite material has a particle size of 1 μm to 100. mu.m.
In a further preferred embodiment of the present invention, the thickness of the thermosetting resin/graphite composite layer is 0.1mm to 0.5mm, and the thickness of the molded plate is less than 1.4 mm.
The invention provides a preparation method of a layered graphite composite bipolar plate, which comprises the following steps:
s1: preparing a thermoplastic resin/graphite composite material plate in a rolling forming mode;
s2: preparing a master batch of the thermosetting resin/graphite composite material;
s3: filling a thermosetting resin/graphite composite material master batch, a thermoplastic resin/graphite composite material plate and a thermosetting resin/graphite composite material master batch into a drying mould in sequence, and drying;
s4: and (5) putting the material dried in the step (S3) and the drying mold into a hot-molding mold, pressurizing, heating and molding, and cooling to obtain the layered graphite composite bipolar plate.
As a preferred embodiment of the present invention, step S1 includes the following processes:
s11: dry-mixing the thermoplastic resin and the graphite powder, uniformly mixing and drying to prepare a master batch A:
s12: keeping the constant feeding rate of the master batch A, and preheating in a preheating box;
s13: and conveying the preheated master batch A by a conveying mechanism, roughly rolling and finely rolling to process the master batch A into a continuous plate with the target thickness, cutting the continuous plate, cooling and cooling to obtain the thermoplastic resin/graphite composite material plate.
The layered structures of the intermediate layer and the surface layer respectively realize the performance requirements of the graphite composite bipolar plate on structural strength, air tightness, in-plane conductivity and reliable forming, thereby realizing the overall optimization of the performance of the plate. Meanwhile, the intermediate layer is used as a substrate auxiliary surface layer for forming, so that the forming difficulty of the ultrathin graphite composite polar plate is reduced.
The composite material is pressed into a plate with a smooth surface by a rolling mode and is used as an intermediate layer of the graphite composite bipolar plate. The roll forming has high production speed, controls the thickness of the middle layer accurately and is suitable for being used as a process mode of batch production.
The composite material required by the middle layer needs to meet multiple functions, and has good fluidity, reliable molding and small molding shrinkage rate in the rolling process; the formed plate needs to have higher air tightness, bending strength and through surface conductivity. In order to satisfy the above functions, a relatively strict requirement should be imposed on the ratio of the thermoplastic resin to the graphite.
As a further preferred embodiment of the present invention, in step S1, the feed rate of the master batch a and the conveying rate of the conveying mechanism are adjusted according to the fluidity of the thermoplastic resin in the master batch a and the content of the graphite powder. If the thermoplastic resin in the master batch A has low fluidity or the graphite content is high, the feeding rate is reduced, and meanwhile, the conveying rate of the conveying mechanism is correspondingly reduced; if the resin fluidity is high or the graphite content is low in the master batch a, the feed rate and the transfer rate are increased.
As a further preferred embodiment of the present invention, in step S1, the preheating temperature of the master batch a is adjusted according to the kind of thermoplastic resin in the master batch a and the content of graphite powder.
As a further preferred embodiment of the present invention, in step S1, the rough rolling and finish rolling are performed by a combination roll group in which horizontal rolls and vertical rolls are combined, and the horizontal rolls and the vertical rolls perform the processing for the thickness and width of the formed plate material, respectively.
In a further preferred embodiment of the present invention, the finish rolling process may be performed by 3 to 10 sets of finishing rolls, depending on the kind of the thermoplastic resin and the content of the graphite powder in the master batch a in step S1. If the content of the thermoplastic resin in the master batch A is greater than that of the graphite, the finish rolling process can be completed by 3-6 groups of finish rolling roller sets, and particularly the high-temperature fluidity of the resin can be adjusted, so that the production efficiency is improved. If the content of the graphite in the master batch A is larger than that of the thermoplastic resin, the finish rolling process can be completed by 7-10 groups of finish rolling roller groups, and reliable forming is ensured.
In a further preferred embodiment of the present invention, in step S1, the continuous sheet material is cut into a sheet material having a target length by the stopper roller.
The surface layer should have high electrical and thermal conductivity after the formation of the plate, and therefore, a high graphite content should be required in the surface layer. On this basis, the surface layer needs to be kept low in thickness while being reliably formed. Therefore, the mixing mode of the thermosetting resin and the graphite is to combine the solvent to carry out mechanical stirring and ultrasonic dispersion so as to ensure that the resin and the graphite are uniformly mixed as much as possible. The amount of solvent is required to take the dispersing effect and easy drying of the graphite into account. In order to meet the performance requirements, the proportion of resin, graphite and solvent is strictly controlled.
As a preferred embodiment of the present invention, in step S2, a solvent and a graphite material are sequentially added to a thermosetting resin and sufficiently mixed to obtain a master batch of a thermosetting resin/graphite composite material;
the solvent is a volatile polar solvent and comprises acetone, and/or absolute ethyl alcohol, and/or n-butyl alcohol, and/or ethylene glycol, and/or isopropanol;
the ratio of the mass of the solvent to the total mass of the thermosetting resin and the graphite material is 1:9-2: 8.
And (3) drying the raw materials of the intermediate layer and the surface layer together in a drying mould, and then carrying out hot compression molding to obtain the layered graphite composite bipolar plate. The preforming method can not only conveniently and efficiently control the feeding amount of the surface layer, but also quickly realize the uniform distribution of the master batch in the die before die pressing, and is beneficial to improving the production efficiency.
In a preferred embodiment of the present invention, the drying process in step S3 is vacuum drying at 80 ℃ for 1-2 h.
In a preferred embodiment of the present invention, in step S3, the masterbatch of thermosetting resin/graphite composite material is vibrated before the drying process to achieve uniform distribution of the masterbatch of thermosetting resin/graphite composite material in the drying mold, and the filling thickness of the masterbatch of thermosetting resin/graphite composite material after the vibration is 0.8mm to 2.0 mm.
As a preferred embodiment of the invention, in the step S4, in the pressure heating forming process, firstly, pre-pressing for 1min at the pressure of 1MPa-10MPa, then, the mould pressing temperature is increased to 140-180 ℃, the forming pressure of hot mould pressing is increased to 15MPa-30 MPa, and the pressure is maintained for 0.5h-1 h; cooling and demoulding to obtain the layered graphite composite bipolar plate. By using GBT20042.6 standard test, the hydrogen permeability coefficient of the polar plate obtained by the invention is less than 1 multiplied by 10-14cm3/(s·cm2Pa), the bending strength is between 50 and 90MPa, and the conductivity is 180S/cm.
According to the invention, the intermediate layer is made of the thermoplastic composite material, so that the feeding precision of the thermosetting composite material is improved in the manufacturing process in an auxiliary manner, and the problem of low molding reliability of the thermosetting composite material under high carbon content is solved; in addition, the middle layer with high resin content in the layered polar plate improves the bending strength and air tightness of the bipolar plate, and the surface layer with high carbon content improves the electrical conductivity of the bipolar plate; the improvement of the overall performance of the bipolar plate is realized by respectively optimizing different functional layers, and meanwhile, the preparation process is simple and convenient, is beneficial to batch production and has higher practical value.
In a third aspect, the present invention provides a system for processing a layered graphite composite bipolar plate, the system comprising:
the middle layer processing device is used for processing the middle layer and is provided with a conveying mechanism for conveying a middle layer material, and a feeding machine, a preheating box, a rough roller set, a finish roller set, a limit roller set and a cooling mechanism which are sequentially arranged along the conveying direction of the conveying mechanism,
a drying device which is provided with a drying box and a drying mould, wherein the drying mould is used for containing the surface layer material and the middle layer,
and the forming device is provided with a hot die pressing mold with a runner structure and is used for hot die pressing and forming the surface layer material and the middle layer which are contained in the drying mold.
In a preferred embodiment of the present invention, the conveying mechanism is a conveyor belt, and the feeder, the preheating box, the rough roller set, the fine roller set, the limit roller set and the cooling mechanism are sequentially arranged on the conveyor belt along a conveying direction of the conveyor belt.
In a preferred embodiment of the present invention, the feeder is a vibrating feeder.
In a preferred embodiment of the present invention, the finishing roll group is provided in plurality, and is disposed in sequence along a conveying direction of the conveying mechanism, for gradually thinning the intermediate layer material on the conveying mechanism.
In a preferred embodiment of the present invention, a plurality of tooth mechanisms are circumferentially distributed on the roller body of the limiting roller set.
In a preferred embodiment of the present invention, the cooling mechanism is an air-cooling type cooling mechanism having a cooling air duct facing the transport mechanism.
As a preferred embodiment of the invention, the drying mold is provided with side walls and a detachable bottom plate. The bottom plate is removed during hot embossing.
Compared with the prior art, the invention respectively meets the requirements of the graphite composite bipolar plate on low thickness (volume), high air tightness, high structural strength, good conductivity, low processing difficulty and the like through the layered structure, thereby realizing the combination of the manufacturability and the practicability of the composite graphite bipolar plate. The composite material with the thermoplastic resin as the substrate has good processability, and thinner plates can be quickly processed by a rolling process. The intermediate layer is prepared from the graphite/thermoplastic resin composite material, so that the processing difficulty is low, and the intermediate layer is used as a substrate, so that the process difficulty of forming the ultrathin sheet by using the thermosetting resin composite material can be reduced. In the bipolar plate, the higher resin content of the intermediate layer can improve the air tightness and structural strength of the bipolar plate. The thermosetting resin/graphite composite material is used as a surface layer, so that the polar plate can have higher in-plane conductivity, and meanwhile, the flow field deformation caused by local high temperature in the use process is avoided, and the long-term reliable operation of the polar plate is ensured. The preparation process is simple and suitable for batch production.
Drawings
FIG. 1 is a schematic cross-sectional view of a layered graphite composite bipolar plate formed according to the present invention.
Fig. 2 is a schematic flow chart illustrating the manufacturing process of the layered graphite composite bipolar plate according to an embodiment of the present invention.
Fig. 3 is a schematic view of an intermediate layer processing apparatus (embodying the processing of the intermediate layer) of the present invention.
Fig. 4 is a schematic view of the hot press molding process of the layered graphite composite bipolar plate of the present invention.
In the figure, 101 is an intermediate layer, 102 is a surface layer, 103 is a runner structure, 201 is a feeder, 202 is a feed valve, 203 is a preheating box, 204 is a roughing roller set, 205 is a finishing roller set, 206 is a limit roller set, 207 is a cooling mechanism, 208 is a conveying mechanism, 301 is a hot-molding die, 302 is a drying die, and 303 is a surface layer material.
Detailed Description
A layered graphite composite bipolar plate, as shown in FIG. 1, comprises an intermediate layer 101 and surface layers 102 disposed on both sides of the intermediate layer 101, wherein the intermediate layer 101 is a thermoplastic resin/graphite composite plate, the surface layers 102 are thermosetting resin/graphite composite layers, and the outer surfaces of the surface layers 102 have flow channel structures 103.
The flow channel structure 103 is preferably formed by hot-molding and curing on the surface layer 102, and has a depth smaller than the thickness of the surface layer 102, and the intermediate layer 101 is a planar structure and does not participate in the flow channel formation. The structure can effectively play the function of ensuring the bending strength of the pole plate by the middle layer 101, can realize the aim of improving the forming precision of the flow channel structure 103 only by optimizing the formula of the surface layer 102, is convenient for the formula optimization of the layered composite pole plate, and provides a solution for solving the problem that the forming performance and the service performance are difficult to take into account.
In the invention, the thermoplastic resin/graphite composite material plate is preferably formed by processing and molding a composite material made of thermoplastic resin and a graphite material. Further preferred thermoplastic resins include fluorinated ethylene-propylene (FEP), and/or polypropylene (PP), and/or Polyphenylene Sulfide (PPs), and/or polyvinylidene fluoride (PVDF), and/or Polycarbonate (PC), and/or polyoxymethylene resin (POM). It is further preferred that the graphite material comprises natural crystalline flake graphite, and/or expanded graphite, and/or carbon fiber powder, and/or chopped carbon fiber. For example, the thermoplastic resin may be fluorinated ethylene-propylene (FEP), and the graphite material may be natural flake graphite. Or thermoplastic resin is selected from fluorinated ethylene-propylene (FEP) and polypropylene (PP) which are mixed according to the proportion of 1:1 or other arbitrary proportion, and the graphite material is selected from carbon fiber powder. Or the thermoplastic resin is selected from Polycarbonate (PC), the graphite material is selected from carbon fiber powder and chopped carbon fiber which are mixed according to a ratio of 9:1 or other arbitrary ratios, and the like. More preferably, the mass ratio of the thermoplastic resin to the graphite material may be 3:7 to 7: 3. It is further preferable that the mass ratio of the thermoplastic resin to the graphite material is 5: 5. It is further preferable that the graphite material has a particle size of 1 μm to 200 μm, and when the graphite material contains chopped carbon fibers, the chopped carbon fibers have a length of 1mm to 5 mm. It is further preferable that the particle size of the graphite material is 40 μm to 80 μm. It is further preferable that the thickness of the thermoplastic resin/graphite composite plate is 0.1mm to 0.4 mm. It is further preferable that the thickness of the thermoplastic resin/graphite composite plate is 0.1mm to 0.2 mm.
The preferred thermosetting resin/graphite composite material layer of the present invention is made from a masterbatch of a thermosetting resin and a graphite material mixed together. Preferred graphitic materials include natural flake graphite, and/or expanded graphite, and/or carbon fibers, and/or graphene nanoplatelets, and/or highly conductive carbon black. Preferably the thermosetting resin is a thermosetting resin with a lower curing temperature, comprising an epoxy resin (EP), and/or a phenolic resin (PF), and/or a polyimide resin (PI), and/or a Vinyl Ester Resin (VER), and/or a polybenzoxazine resin (PBA), and/or a urea formaldehyde resin (UR), and/or a polyurethane resin (PU). For example, epoxy resin (EP) is selected as the thermosetting resin, and the graphite material comprises natural flake graphite. Or the thermosetting resin is selected from phenolic resin (PF) and polyimide resin (PI) which are mixed according to the proportion of 1:1 or any other proportion, and the graphite material is selected from graphene nanosheets. Or the thermosetting resin is polyurethane resin (PU), and the graphite material is expanded graphite and carbon fiber which are mixed according to the ratio of 8:2 or other arbitrary ratios. The mass ratio of the thermosetting resin to the graphite material is preferably 7:3-9: 1. The particle size of the graphite material is 1-100 μm. The thickness of the thermosetting resin/graphite composite material layer is more preferably 0.1mm-0.5mm, and the thickness of the formed composite graphite electrode plate is less than 1.4 mm.
A preparation method of a layered graphite composite bipolar plate comprises the following steps:
s1: preparing a thermoplastic resin/graphite composite material plate in a rolling forming mode;
s2: preparing a master batch of the thermosetting resin/graphite composite material;
s3: filling a thermosetting resin/graphite composite material master batch, a thermoplastic resin/graphite composite material plate and a thermosetting resin/graphite composite material master batch into a drying mould in sequence, and drying;
s4: and (5) putting the material dried in the step (S3) and the drying mold into a hot molding mold, pressurizing, heating and molding, and cooling to obtain the layered graphite composite bipolar plate.
Preferably, step S1 includes the following processes:
s11: dry-mixing the thermoplastic resin and the graphite powder, uniformly mixing and drying to prepare a master batch A:
s12: keeping the constant feeding rate of the master batch A, and preheating in a preheating box;
s13: and conveying the preheated master batch A by a conveying mechanism, roughly rolling and finely rolling to process the master batch A into a continuous plate with the target thickness, cutting the continuous plate, cooling and cooling to obtain the thermoplastic resin/graphite composite material plate.
The layered structures of the intermediate layer and the surface layer respectively realize the performance requirements of the graphite composite bipolar plate on structural strength, air tightness, in-plane conductivity and reliable forming, thereby realizing the overall optimization of the performance of the plate. Meanwhile, the intermediate layer is used as a substrate auxiliary surface layer for forming, so that the forming difficulty of the ultrathin graphite composite polar plate is reduced.
The composite material is pressed into a plate with a smooth surface by a rolling mode and is used as an intermediate layer of the graphite composite bipolar plate. The roll forming has high production speed, controls the thickness of the middle layer accurately and is suitable for being used as a process mode of batch production.
The composite material required by the middle layer needs to meet multiple functions, and has good fluidity, reliable molding and small molding shrinkage rate in the rolling process; the formed plate needs to have higher air tightness, bending strength and through surface conductivity. In order to satisfy the above functions, a relatively strict requirement should be imposed on the ratio of the thermoplastic resin to the graphite.
Preferably, in step S1, the feeding rate of the master batch a and the conveying rate of the conveying mechanism are adjusted according to the fluidity of the thermoplastic resin in the master batch a and the content of the graphite powder. If the thermoplastic resin in the master batch A has low fluidity or the graphite content is high, the feeding rate is reduced, and meanwhile, the transmission rate of the transmission mechanism is reduced in response; if the resin fluidity is high or the graphite content is low in the master batch a, the feed rate and the transfer rate are increased. Preferably, in step S1, the preheating temperature of the masterbatch a is adjusted according to the type of thermoplastic resin in the masterbatch a and the content of graphite powder; preferably, in step S1, the rough rolling and finish rolling are performed by a combination roll set composed of a combination of horizontal rolls and vertical rolls, which perform the thickness and width processing of the formed plate, respectively. Preferably, in step S1, the finish rolling process may be performed by 3 to 10 sets of finishing rolls, depending on the kind of thermoplastic resin and the content of graphite powder in the master batch a. If the content of the thermoplastic resin in the master batch A is greater than that of the graphite, the finish rolling process can be completed by 3-6 groups of finish rolling roller sets, and particularly the high-temperature fluidity of the resin can be adjusted, so that the production efficiency is improved. If the content of the graphite in the master batch A is larger than that of the thermoplastic resin, the finish rolling process can be completed by 7-10 groups of finish rolling roller groups, and reliable forming is ensured. Preferably, in step S1, the continuous sheet material is cut by the check roll into a sheet material having a target length.
The surface layer should have high electrical and thermal conductivity after the formation of the plate, and therefore, a high graphite content should be required in the surface layer. On this basis, the surface layer needs to be kept low in thickness while being reliably formed. Therefore, the mixing mode of the thermosetting resin and the graphite is to combine the solvent to carry out mechanical stirring and ultrasonic dispersion so as to ensure that the resin and the graphite are uniformly mixed as much as possible. The amount of solvent is required to take the dispersing effect and easy drying of the graphite into account. In order to meet the performance requirements, the proportion of resin, graphite and solvent is strictly controlled.
Preferably, in step S2, a solvent and a graphite material are sequentially added to the thermosetting resin and fully mixed to obtain a master batch of the thermosetting resin/graphite composite material; the solvent is volatile polar solvent, including acetone, and/or anhydrous alcohol, and/or n-butanol, and/or ethylene glycol, and/or isopropanol; the ratio of the mass of the solvent to the total mass of the thermosetting resin and the graphite material is 1:9-2: 8.
And (3) drying the raw materials of the intermediate layer and the surface layer together in a drying mould, and then carrying out hot compression molding to obtain the layered graphite composite bipolar plate. The preforming method can not only conveniently and efficiently control the feeding amount of the surface layer, but also quickly realize the uniform distribution of the master batch in the die before die pressing, and is beneficial to improving the production efficiency.
Preferably, in step S3, the drying process is vacuum drying at 80 deg.C for 1-2 h. Preferably, in step S3, the masterbatch of the thermosetting resin/graphite composite material is compacted before the drying process to achieve uniform distribution of the masterbatch of the thermosetting resin/graphite composite material in the drying mold, and the filling thickness of the masterbatch of the thermosetting resin/graphite composite material after the compaction is 0.8mm to 2.0 mm.
Preferably, in the step S4, in the pressurizing and heating forming process, firstly, pre-pressing for 1min at the pressure of 1MPa-10MPa, then, the mould pressing temperature is increased to 140-180 ℃, the forming pressure of hot mould pressing is increased to 15MPa-30 MPa, and the pressure is maintained for 0.5h-1 h; cooling and demoulding to obtain the layered graphite composite bipolar plate.
Fig. 2 shows a schematic flow chart of a method for manufacturing a layered graphite composite bipolar plate according to the present invention.
A processing system of a layered graphite composite bipolar plate, as shown in fig. 3-4, comprising an intermediate layer processing device, a drying device and a forming device, wherein: the middle layer processing device is used for processing the middle layer 101, and comprises a conveying mechanism 208 for conveying a middle layer material, and a feeding machine 201, a preheating box 203, a rough roller group 204, a fine roller group 205, a limiting roller group 206 and a cooling mechanism 207 which are sequentially arranged along the conveying direction of the conveying mechanism 208; the drying device is provided with a drying box and a drying mold 302, wherein the drying mold 302 is used for containing the surface layer material 303 and the middle layer 101; the molding apparatus has a hot-molding die 301 with a runner structure for hot-molding the surface layer material 303 and the intermediate layer 101 contained in the drying die 302.
In a preferred embodiment of the present invention, the conveying mechanism 208 is a conveyor belt, and the feeder, the preheating tank, the rough roller set, the fine roller set, the limit roller set, and the cooling mechanism are sequentially disposed on the conveyor belt along a conveying direction of the conveyor belt.
In the invention, the feeding machine 201 is preferably a vibrating feeding machine, and a feeding valve 202 is arranged at the outlet of the vibrating feeding machine. In the present invention, it is preferable that the finishing roll group 205 is provided in plural number, and is provided in sequence along the conveying direction of the conveying mechanism, for gradually thinning the intermediate layer material on the conveying mechanism. According to the invention, a plurality of convex tooth structures are preferably distributed on the roller body of the limiting roller group 206 along the circumferential direction. In the invention, two press rolls of the rough roll set 204, the fine roll set 205 and the limit roll set 206 can be respectively arranged on the upper surface and the lower surface of the conveyor belt and are used for processing materials conveyed on the conveyor belt. The cooling mechanism 207 is preferably an air-cooling type cooling mechanism having a cooling air duct facing the transport mechanism. The drying mold 302 has side walls and a removable bottom plate that is removed during hot molding.
The preheating cabinet 203, the cooling mechanism 207, the drying cabinet and other equipment can adopt corresponding equipment sold in the market.
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1:
preparing a layered graphite composite bipolar plate, comprising the following steps:
(1) fluorinated ethylene-propylene (FEP) having an average particle size of 8 μm and crystalline flake graphite having an average particle size of 50 μm were dry-blended for 2 hours by a plastic kneader, and the mixing ratio by mass of FEP to crystalline flake graphite was 4: 6. And then, putting the mixed master batch into a vacuum drying oven, and drying for 2 hours at the temperature of 70 ℃ to obtain the master batch A.
(2) The master batch a was fed from the vibratory feeder 201 into the preheating tank 203, and as shown in fig. 3, the preheating temperature was 360 ℃.
(3) The master batch A is conveyed to the lower part of a roughing roller by a conveying mechanism 208 and is roughly rolled into a plate with the thickness of 2.0 mm. And finally, finishing the steel plate by 7 times to sequentially process the steel plate into the thickness of 1.5mm, 1.0mm, 0.7mm, 0.5mm, 0.4mm, 0.35mm and 0.3 mm. The roughing and finishing rolls are heated during operation to maintain the roll surface temperature at about 300 c.
(4) The continuous sheet is cut into individual sheets by the lobe configuration on the set of stop rollers 206.
(5) And the cooling mechanism 207 continuously blows clean and dry air, cools the plate through air cooling, and reduces the temperature of the plate to be below 80 ℃ to obtain the intermediate layer.
(6) The thermosetting resin in the master batch B is granular phenolic resin, the graphite material is natural crystalline flake graphite with the grain diameter of 60 mu m, and absolute ethyl alcohol is used as a solvent. Wherein the mass ratio of the resin, the graphite and the solvent is 1:9:1.1, stirring is carried out for 30min by a mechanical stirrer, and then ultrasonic dispersion is carried out for 10 min.
(7) And sequentially filling the master batch B (surface layer material 303), the intermediate layer 101 and the master batch B (surface layer material 303) which are mixed into the drying die 302, wherein the filling thickness of the master batch B is 2.4mm, filling is carried out on a vibrating machine, and vibrating for 1min after filling is finished, so that the master batch B is ensured to be uniformly distributed in the drying die 302. The drying mold 302 was then placed in a vacuum oven and the solvent was removed for 1h at 80 ℃.
(8) The drying mold 302 with the master batch B and the intermediate layer 101 therein is placed in a hot-molding mold 301, as shown in fig. 4. And then heating to 180 ℃, raising the pressure to 20MPa, keeping for 1h, then keeping the die assembly and removing the pressure to carry out water cooling on the hot die-pressing die, and demoulding after the temperature is reduced to below 60 ℃ to obtain the layered graphite composite bipolar plate. The thickness of the formed plate is 1.2 plus or minus 0.04mm, wherein the thickness of the surface layer is 0.45 plus or minus 0.02mm, and the depth of the flow channel is 0.35 plus or minus 0.01 mm.
Example 2:
preparing a layered graphite composite bipolar plate, comprising the following steps:
(1) based on example 1, the fabrication of the interlayer was completed.
(2) Liquid epoxy resin (E-44) and curing agent phthalic anhydride (HHPA) were preheated to 110 deg.C separately and held for 2 min.
(3) Weighing the epoxy resin and HHPA according to the mass ratio of 5:4, pouring the epoxy resin and the HHPA into a beaker at the same temperature, stirring for 5min, and taking benzyl methyl dimethylamine which is 0.5 percent of the mass of the epoxy resin and is taken as an accelerator during stirring to be added into the epoxy resin.
(4) Adding crystalline flake graphite into the uniformly mixed resin, wherein the particle size is 60-80 mu m. The mass ratio of the resin to the graphite mixture was 2: 8. Keeping the temperature at 110 ℃, and mechanically stirring for 20min until the master batch B is obtained after uniform mixing.
(5) And sequentially adding the master batch B, the intermediate layer 101 and the master batch B into a drying die, wherein the filling thickness of the master batch B in the drying die is 1mm, and semi-curing at 110 ℃ for 30min in an air drying oven.
(6) Laying a PTFE film in a hot molding die 301 as an auxiliary demolding, putting a drying die 302 and materials in the drying die into the hot molding die preheated to 110 ℃, pressurizing to 30MPa for 5min, then removing the pressure, heating to 120 ℃, and preserving heat for 90 min.
(7) And taking out the shaped composite bipolar plate sample, putting the sample into a blast drying oven, preserving heat for 2 hours at 180 ℃ to further finish curing, and obtaining the layered ultrathin graphite composite bipolar plate after curing. The thickness of the formed plate is 0.9 plus or minus 0.04mm, the thickness of the surface layer is 0.3 plus or minus 0.02mm, and the depth of the flow channel is 0.25 plus or minus 0.01 mm.
Example 3
The preparation method of the layered ultrathin graphite composite bipolar plate comprises the following steps:
(1) polypropylene (PP) with the average particle size of 8 mu m and carbon fiber powder with the average length of 100 mu m are dry-mixed for 2h by a ball mill, and the mixing mass ratio of the PP to the carbon fiber is 5: 5. And then, putting the mixed master batch into a vacuum drying oven, and drying for 5 hours at the temperature of 70 ℃ to obtain the master batch A.
(2) The masterbatch A was fed from a vibratory feeder 201 into a filler preheating tank 203, and as shown in FIG. 3, the preheating temperature was 200 ℃.
(3) The master batch A is conveyed to the lower part of the rough roller group 204 by the conveying mechanism 208 and is roughly rolled into a plate with the thickness of 1.5 mm. And finally, finishing the steel plate by 4 times of finish rolling to sequentially process the steel plate into the thickness of 1.0mm, 0.6mm, 0.2mm and 0.1 mm. The rough roll-set 204 and the finish roll-set 205 are heated during operation to maintain the roll surface temperature at about 170 c.
(4) The continuous sheet is cut into individual sheets by the lobe configuration on the set of stop rollers 206.
(5) The cooling mechanism 207 continuously blows clean and dry air, cools the plate through air cooling, and cools the plate to room temperature to obtain the intermediate layer.
(6) The thermosetting resin in the master batch B is granular phenolic resin, the graphite material is natural crystalline flake graphite with the grain diameter of 60 mu m, and absolute ethyl alcohol is used as a solvent. Wherein the mass ratio of the resin, the graphite and the solvent is 2:8:1.5, stirring is carried out for 30min by a mechanical stirrer, and then ultrasonic dispersion is carried out for 10 min.
(7) And filling the mixed master batch B, the intermediate layer 101 and the master batch B into a drying die 302 in sequence, wherein the filling thickness of the master batch B is 2.0mm, filling on a vibrating machine, and vibrating for 1min after filling is finished to ensure that the master batch B is uniformly distributed in the drying die 302. The drying mold 302 is then placed in a vacuum drying oven and the solvent is removed for 90min at 70 ℃.
(8) The dry mold 302 with the master batch B303 and the intermediate layer 101 therein was placed in a hot-molded mold as shown in fig. 4. And then heating to 180 ℃, raising the pressure to 30MPa, keeping for 1h, then keeping the die assembly and removing the pressure to carry out water cooling on the hot die-pressing die, and demoulding after the temperature is reduced to below 60 ℃ to obtain the layered ultrathin graphite composite bipolar plate. The thickness of the formed plate is 0.8 plus or minus 0.04mm, wherein the thickness of the surface layer is 0.35 plus or minus 0.02mm, and the depth of the flow channel is 0.25 plus or minus 0.01 mm.
By using GBT20042.6 standard test, the hydrogen permeability coefficient of the polar plate obtained by the invention is less than 1 multiplied by 10-14cm3/(s·cm2Pa), the bending strength is between 50 and 90MPa, and the conductivity is 180S/cm.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A layered graphite composite bipolar plate is characterized by comprising an intermediate layer and surface layers arranged on two sides of the intermediate layer, wherein the intermediate layer is a thermoplastic resin/graphite composite material plate, the surface layers are thermosetting resin/graphite composite material layers, and the outer surfaces of the surface layers are subjected to thermosetting molding to form a flow channel structure.
2. A layered graphite composite bipolar plate as claimed in claim 1, wherein said thermoplastic resin/graphite composite sheet is formed from a composite of thermoplastic resin and graphite material, including any one or more of the following conditions:
(i) the thermoplastic resin comprises fluorinated ethylene-propylene, and/or polypropylene, and/or polyphenylene sulfide, and/or polyvinylidene fluoride, and/or polycarbonate, and/or polyformaldehyde resin;
(ii) the graphite material comprises natural crystalline flake graphite, and/or expanded graphite, and/or carbon fiber powder, and/or chopped carbon fiber.
3. A layered graphite composite bipolar plate according to claim 2, wherein said thermoplastic resin/graphite composite sheet comprises any one or more of the following conditions:
(i) the mass ratio of the thermoplastic resin to the graphite material is 3:7-7: 3;
(ii) the particle size of the graphite material is 1-200 μm, and when the graphite material contains chopped carbon fibers, the length of the chopped carbon fibers is 1-5 mm;
(iii) the thickness of the thermoplastic resin/graphite composite material plate is 0.1mm-0.4 mm.
4. A layered graphite composite bipolar plate as claimed in claim 1, wherein said thermosetting resin/graphite composite layer is made from a masterbatch of a thermosetting resin and a graphite material mixed together, including any one or more of the following conditions:
(i) the graphite material comprises natural crystalline flake graphite, and/or expanded graphite, and/or carbon fiber, and/or graphene nanosheet, and/or highly conductive carbon black;
(ii) the thermosetting resin is thermosetting resin with lower curing temperature, and comprises epoxy resin, and/or phenolic resin, and/or polyimide resin, and/or vinyl ester resin, and/or polybenzoxazine resin, and/or urea-formaldehyde resin, and/or polyurethane resin.
5. A layered graphite composite bipolar plate according to claim 4, wherein said thermosetting resin/graphite composite layer comprises any one or more of the following conditions:
(i) the mass ratio of the graphite material to the thermosetting resin is 7:3-9: 1;
(ii) the particle size of the graphite material is 1-100 μm;
(iii) the thickness of the thermosetting resin/graphite composite material layer is 0.1mm-0.5mm, and the thickness of the molding electrode plate is less than 1.4 mm.
6. A method of making a layered graphite composite bipolar plate according to claim 1, comprising the steps of:
s1: preparing a thermoplastic resin/graphite composite material plate in a rolling forming mode;
s2: preparing a master batch of the thermosetting resin/graphite composite material;
s3: filling a thermosetting resin/graphite composite material master batch, a thermoplastic resin/graphite composite material plate and a thermosetting resin/graphite composite material master batch into a drying mould in sequence, and drying;
s4: and (5) putting the material dried in the step (S3) and the drying mold into a hot-molding mold, pressurizing, heating and molding, and cooling to obtain the layered graphite composite bipolar plate.
7. The method of claim 6, wherein step S1 comprises the following steps:
s11: dry-mixing the thermoplastic resin and the graphite powder, uniformly mixing and drying to prepare a master batch A:
s12: keeping the constant feeding rate of the master batch A, and preheating in a preheating box;
s13: and conveying the preheated master batch A by a conveying mechanism, roughly rolling and finely rolling to process the master batch A into a continuous plate with the target thickness, cutting the continuous plate, cooling and cooling to obtain the thermoplastic resin/graphite composite material plate.
8. The method of claim 7, wherein step S1 includes any one or more of the following conditions:
(i) the feeding rate of the master batch A and the conveying rate of the conveying mechanism are adjusted according to the fluidity of the thermoplastic resin in the master batch A and the content of the graphite powder;
(ii) the preheating temperature of the master batch A is adjusted according to the type of the thermoplastic resin in the master batch A and the content of the graphite powder;
(iii) the rough rolling and the finish rolling are completed by a combined roller set formed by combining a horizontal roller and a vertical roller, and the horizontal roller and the vertical roller respectively realize the processing of the thickness and the width of the formed plate;
(iii) according to the type of the thermoplastic resin and the content of the graphite powder in the master batch A, the finish rolling process can be completed by 3-10 groups of finish rolling roller groups;
(iv) the continuous sheet material is cut into a sheet material having a target length by a stopper roller.
9. The method of claim 6, wherein in step S2, the thermosetting resin/graphite composite material master batch is obtained by adding the solvent and the graphite material to the thermosetting resin in sequence and mixing them thoroughly;
the solvent is a volatile polar solvent and comprises acetone, and/or absolute ethyl alcohol, and/or n-butyl alcohol, and/or ethylene glycol, and/or isopropanol;
the ratio of the mass of the solvent to the total mass of the thermosetting resin and the graphite material is 1:9-2: 8.
10. A method of making a layered graphite composite bipolar plate as claimed in claim 6, comprising any one or more of the following conditions:
(i) in the step S3, the drying treatment is vacuum drying for 1h-2h at the temperature of 80 ℃;
(ii) in step S3, before the drying treatment, the master batch of the thermosetting resin/graphite composite material is vibrated to realize the uniform distribution of the master batch of the thermosetting resin/graphite composite material in the drying mold, and the filling thickness of the master batch of the thermosetting resin/graphite composite material after the vibration is 0.8mm to 2.0 mm;
(iii) in the step S4, in the pressurizing and heating forming process, firstly, prepressing for 1min at the pressure of 1MPa-10MPa, then raising the mould pressing temperature to 140-180 ℃, raising the forming pressure of hot mould pressing to 15MPa-30 MPa, and keeping for 0.5h-1 h; cooling and demoulding to obtain the layered graphite composite bipolar plate.
CN202010734155.3A 2020-07-27 2020-07-27 Layered graphite composite bipolar plate and preparation method thereof Pending CN111883794A (en)

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