CN113113627A - Composite flexible graphite polar plate preparation method and composite flexible graphite polar plate prepared by same - Google Patents
Composite flexible graphite polar plate preparation method and composite flexible graphite polar plate prepared by same Download PDFInfo
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- CN113113627A CN113113627A CN202010031589.7A CN202010031589A CN113113627A CN 113113627 A CN113113627 A CN 113113627A CN 202010031589 A CN202010031589 A CN 202010031589A CN 113113627 A CN113113627 A CN 113113627A
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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
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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
- H01M8/0213—Gas-impermeable carbon-containing materials
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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
- H01M8/0221—Organic resins; Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
The application provides a preparation method of a composite flexible graphite polar plate and the prepared composite flexible graphite polar plate, and the method comprises the following steps: pressing the expanded graphite worms into porous graphite paper; mixing and stirring the carbon microspheres and resin to obtain carbon microsphere/resin conductive slurry; alternately laminating the porous graphite paper and the electroconductive paste to obtain an electroconductive paste/porous graphite paper laminate; and rolling and printing the laminated body to obtain the composite flexible graphite pole plate. The method can effectively improve the air tightness, the electric and heat conduction capability and the mechanical strength of the graphite polar plate, greatly shorten the preparation time of the polar plate, improve the plate manufacturing efficiency and is suitable for large-scale application.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a preparation method of a composite flexible graphite polar plate and the composite flexible graphite polar plate prepared by the same.
Background
The fuel cell is not limited by the cycle of the Carnot heat engine, can generate electricity as long as fuel is provided, has the advantages of high energy conversion rate, no pollution, low noise, high reliability and the like, and is considered as a preferred, clean and efficient power generation technology in the 21 st century. Currently, research on fuel cells by governments and enterprises of various countries is mainly focused on Proton Exchange Membrane Fuel Cells (PEMFCs), and has obtained a major breakthrough. However, the cost still is a main problem that restricts the PEMFC from entering the market, and the bipolar plate as the main component of the PEMFC not only accounts for 70% of the total weight of the fuel cell in terms of cost, but also accounts for 30-45% of the total weight of the fuel cell in terms of cost, so that the search for a bipolar plate with excellent performance and low price is urgent.
Up to now, fuel cell bipolar plates are mainly classified into three major categories, namely, graphite plates, metal plates, and graphite-resin composite plates. The graphite bipolar plate is a commercial bipolar plate which is mature at present, has the characteristics of high strength and good air tightness, but has the disadvantages of complex process, long production period and high cost, and is not beneficial to large-scale production; the metal plate has excellent mechanical property, electrical conductivity and thermal conductivity, but has poor corrosion resistance, and the practical application of the metal bipolar plate is severely restricted; the graphite-resin composite plate is a composite bipolar plate prepared by compounding graphite serving as a conductive material, resin serving as a binder and a reinforcing agent, has the advantages of low cost, high production efficiency, easiness in mass production, corrosion resistance and the like, and is the main development direction of the bipolar plate in the future.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the method for preparing the composite flexible graphite pole plate and the composite flexible graphite pole plate prepared by the method can effectively improve the air tightness, the electric and heat conduction capability and the mechanical strength of the graphite pole plate, greatly shorten the preparation time of the pole plate, improve the plate preparation efficiency and are suitable for large-scale application.
In order to achieve the above object, the present application provides a method for preparing a composite flexible graphite electrode plate, comprising: pressing the expanded graphite worms into porous graphite paper; mixing and stirring the carbon microspheres and resin to obtain carbon microsphere/resin conductive slurry; alternately laminating the porous graphite paper and the electroconductive paste to obtain an electroconductive paste/porous graphite paper laminate; and rolling and printing the laminated body to obtain the composite flexible graphite pole plate.
Further, alternately laminating the porous graphite paper and the electroconductive paste to obtain an electroconductive paste/porous graphite paper laminate comprises repeatedly performing the following operations until the porous graphite paper reaches a predetermined number of layers: uniformly coating the conductive slurry on the surface of the porous graphite paper; and covering the other piece of porous graphite paper on the conductive slurry.
Further, in the step of pressing the expanded graphite worms into the porous graphite paper, the thickness of the porous graphite paper is 0.4-1 mm.
Further, in the step of pressing the expanded graphite worms into the porous graphite paper, the density of the porous graphite paper is 0.2-0.6 g/cm3。
Further, in the step of mixing and stirring the carbon microspheres and the resin to obtain the carbon microsphere/resin conductive slurry, the mass ratio of the carbon microspheres to the resin is 10-30%.
Further, the carbon microspheres are micron-sized carbon microspheres.
Further, in the step of alternately laminating the porous graphite paper and the conductive paste to obtain the conductive paste/porous graphite paper laminated body, the number of layers of the porous graphite paper is 4-8.
Further, in the step of alternately laminating the porous graphite paper and the electroconductive paste to obtain an electroconductive paste/porous graphite paper laminate, the mass ratio of the electroconductive paste to the porous graphite paper is 50% to 150%.
The application also provides a composite flexible graphite polar plate, which is prepared by adopting the preparation method of the composite flexible graphite polar plate.
Compared with the prior art, the preparation method of the composite flexible graphite polar plate has the following advantages:
(1) the graphite microspheres can be embedded and filled in gaps of the graphite paper, so that contact points among graphite sheet layers are increased, and the air tightness, the electric conduction and the heat conduction of the graphite polar plate are improved;
(2) the resin in the conductive slurry flows into the pores of the graphite paper under the action of pressure, and the mechanical strength of the graphite polar plate can be effectively improved through the combined action of the resin and the carbon microspheres;
(3) the rolling process can greatly shorten the preparation time of the polar plate, improve the plate manufacturing efficiency and is suitable for large-scale application.
The composite flexible graphite polar plate prepared by the method has excellent air tightness, electric and thermal conductivity and mechanical properties, and is short in preparation period, high in production efficiency and suitable for large-scale application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a flow diagram of a method of making a composite flexible graphite plate according to an embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
Fig. 1 shows a flow diagram of a method of making a composite flexible graphite plate according to an embodiment of the present application. A method of making a composite flexible graphite electrode plate according to an embodiment of the present application is described below with reference to fig. 1.
As shown in fig. 1, the present application provides a method for preparing a composite flexible graphite plate, aiming at the problems of poor air tightness and thermal conductivity, low mechanical strength, long production cycle, etc. existing in the existing flexible graphite plate, comprising:
s110: pressing the expanded graphite worms into porous graphite paper;
s120: mixing and stirring the carbon microspheres and resin to obtain carbon microsphere/resin conductive slurry;
s130: alternately laminating the porous graphite paper and the electroconductive paste to obtain an electroconductive paste/porous graphite paper laminate;
s140: and rolling and printing the laminated body to obtain the composite flexible graphite pole plate.
The graphite paper pressed in step S110 is loose porous low-density graphite paper, the thickness is preferably 0.4-1 mm, and the density is preferably 0.2-0.6 g/cm3. Gaps and pores exist in the loose and porous graphite paper, so that the graphite microspheres can be embedded and filled in the gaps of the graphite paper in the subsequent step, and the resin in the conductive slurry can flow into the pores of the graphite paper under the action of pressure.
In step S120, mixing the carbon microspheres and the resin, and uniformly stirring to obtain the carbon microsphere/resin conductive paste, wherein the mass ratio of the carbon microspheres to the resin is preferably 10-30%. The carbon microspheres are preferably micron-sized carbon microspheres.
In step S130, the conductive paste is uniformly coated on the surface of the porous graphite paper, a layer of graphite paper is further covered on the surface of the porous graphite paper coated with the conductive paste, and the above operations are repeated until the number of the porous graphite paper reaches a predetermined number, so as to obtain a conductive paste/porous graphite paper laminated body. The conductive paste/porous graphite paper laminate includes a predetermined number of layers of porous graphite paper and a conductive paste between each adjacent two layers of porous graphite paper. The number of layers of the porous graphite paper is preferably 4-8, and the mass ratio of the conductive paste to the porous graphite paper is preferably 50-150%.
In step S140, the conductive paste/porous graphite paper laminate is subjected to roll printing, and the graphite paper is compressed from a low-density state to a high-density state, so as to obtain the flexible graphite electrode plate with a flow channel. Compared with a mould pressing process, the rolling process can greatly shorten the preparation time of the polar plate, improve the plate manufacturing efficiency and is suitable for large-scale application.
Through stratifying porous graphite paper and carbosphere/resin conductive paste and carrying out the roll-in, the graphite microballon can be embedded and fill in the clearance of graphite paper to increase the contact site between the graphite lamella, improve the gas tightness and electrically conductive and heat conductivity of graphite polar plate, and the resin in the conductive paste can flow under the pressure effect and get into in the hole of graphite paper, through the combined action with the carbosphere, can effectively improve the mechanical strength of graphite polar plate.
According to the preparation method of the composite flexible graphite polar plate, firstly, expanded graphite worms are pressed into porous graphite paper, then, carbon microspheres and resin are mixed and uniformly stirred to obtain carbon microsphere/resin conductive slurry, then, the conductive slurry is uniformly coated on the surface of the low-density porous graphite paper, a layer of porous graphite paper is further covered on the surface of the conductive slurry-coated porous graphite paper, the above operations are repeated to obtain a conductive slurry/porous graphite paper laminated body, finally, the conductive slurry/porous graphite paper laminated body is subjected to roll printing, and the graphite paper is compressed from a low-density state to a high-density state to obtain the flexible graphite polar plate with a flow channel. In the method, the graphite paper in a low-density state has a loose and porous structure, and the graphite paper is compressed when the laminated body is rolled, and meanwhile, on one hand, graphite microspheres can be embedded and filled in gaps of the graphite paper, so that contact sites between graphite sheet layers are increased, and the air tightness, the electric conduction and the heat conduction of the graphite polar plate are improved; on the other hand, the resin in the conductive slurry flows into the pores of the graphite paper under the action of pressure, and the mechanical strength of the graphite polar plate can be effectively improved through the combined action of the resin and the carbon microspheres. In addition, compared with a die pressing process, the preparation time of the polar plate can be greatly shortened by utilizing a rolling process, the plate manufacturing efficiency is improved, and the method is suitable for large-scale application.
A specific example of the composite flexible graphite electrode plate production method of the present application is described in detail below with reference to fig. 1.
First embodiment
S110: pressing the expanded graphite into a density of 0.2g/cm3Porous graphite paper with the thickness of 0.4 mm;
s120: mixing the carbon microspheres and the resin according to the mass ratio of 10%, and uniformly stirring to obtain carbon microsphere/resin conductive slurry;
s130: uniformly coating the conductive paste in the step S120 on the surface of the graphite paper in the step S110, wherein the mass ratio of the conductive paste to the graphite paper is 50%, covering another piece of graphite paper on the conductive paste, and repeating the operation to obtain a conductive paste/graphite paper laminated body containing 4 layers of graphite paper;
s140: and (4) rolling and printing the laminated body in the step (S130) to obtain the qualified composite flexible graphite pole plate.
Second embodiment
S110: pressing the expanded graphite into a density of 0.4g/cm3Porous graphite paper with the thickness of 0.7 mm;
s120: mixing the carbon microspheres and the resin according to the mass ratio of 20%, and uniformly stirring to obtain carbon microsphere/resin conductive slurry;
s130: uniformly coating the conductive paste in the step S120 on the surface of the graphite paper in the step S110, wherein the mass ratio of the conductive paste to the graphite paper is 100%, covering another piece of graphite paper on the conductive paste, and repeating the operation to obtain a conductive paste/graphite paper laminated body containing 6 layers of graphite paper;
s140: and (4) rolling and printing the laminated body in the step (S130) to obtain the qualified composite flexible graphite pole plate.
Third embodiment
S110: pressing the expanded graphite into a density of 0.6g/cm3Porous graphite paper with the thickness of 1 mm;
s120: mixing the carbon microspheres and the resin according to the mass ratio of 30%, and uniformly stirring to obtain carbon microsphere/resin conductive slurry;
s130: uniformly coating the conductive paste in the step S120 on the surface of the graphite paper in the step S110, wherein the mass ratio of the conductive paste to the graphite paper is 150%, covering another piece of graphite paper on the conductive paste, and repeating the operation to obtain a conductive paste/graphite paper laminated body containing 8 layers of graphite paper;
s140: and (4) rolling and printing the laminated body in the step (S130) to obtain the qualified composite flexible graphite pole plate.
According to the embodiment of the application, the composite flexible graphite pole plate is prepared by adopting the preparation method of the composite flexible graphite pole plate.
The composite flexible graphite polar plate provided by the invention has the advantages of excellent air tightness, electric and thermal conductivity and mechanical properties, short preparation period, high production efficiency and suitability for large-scale application.
In the description of the present application, it is to be understood that the orientation or positional relationship indicated by the directional terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal" and "top, bottom", etc., are generally based on the orientation or positional relationship shown in the drawings, and are used for convenience of description and simplicity of description only, and in the case of not making a reverse description, these directional terms do not indicate and imply that the device or element being referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore, should not be considered as limiting the scope of the present application; the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.
Spatially relative terms, such as "above … …," "above … …," "above … …," "above," and the like, may be used herein for ease of description to describe one device or feature's spatial relationship to another device or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is turned over, devices described as "above" or "on" other devices or configurations would then be oriented "below" or "under" the other devices or configurations. Thus, the exemplary term "above … …" can include both an orientation of "above … …" and "below … …". The device may be otherwise variously oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
It should be noted that the terms "first", "second", and the like are used to define the components, and are only used for convenience of distinguishing the corresponding components, and the terms have no special meanings unless otherwise stated, and therefore, the scope of protection of the present application is not to be construed as being limited.
It should be understood that the various steps or sub-steps of the methods described above are not necessarily performed in sequential order. The steps are not performed in the exact order shown and described, and may be performed in other orders, unless explicitly stated otherwise. Moreover, at least a portion of the steps described above may include multiple sub-steps or multiple stages that are not necessarily performed at the same time, but may be performed at different times, and the order of performance of the sub-steps or stages is not necessarily sequential, but may be performed alternately or in alternation with other steps or at least a portion of the sub-steps or stages of other steps.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (9)
1. A preparation method of a composite flexible graphite pole plate is characterized by comprising the following steps:
pressing the expanded graphite worms into porous graphite paper;
mixing and stirring the carbon microspheres and resin to obtain carbon microsphere/resin conductive slurry;
alternately laminating the porous graphite paper and the electroconductive paste to obtain an electroconductive paste/porous graphite paper laminate;
and rolling and printing the laminated body to obtain the composite flexible graphite pole plate.
2. The method of making a composite flexible graphite plate of claim 1, wherein alternately laminating the porous graphite paper and the electrically conductive paste to obtain an electrically conductive paste/porous graphite paper laminate comprises repeating the following operations until the porous graphite paper reaches a predetermined number of layers:
uniformly coating the conductive slurry on the surface of the porous graphite paper;
and covering the other piece of porous graphite paper on the conductive slurry.
3. The method for preparing a composite flexible graphite plate according to claim 1, wherein in the step of pressing the expanded graphite worms into the porous graphite paper, the thickness of the porous graphite paper is 0.4-1 mm.
4. The method for preparing a composite flexible graphite plate as claimed in claim 1, wherein in the step of pressing the expanded graphite worms into the porous graphite paper, the density of the porous graphite paper is 0.2-0.6 g/cm3。
5. The method for preparing the composite flexible graphite plate according to claim 1, wherein in the step of mixing and stirring the carbon microspheres and the resin to obtain the carbon microsphere/resin conductive slurry, the mass ratio of the carbon microspheres to the resin is 10-30%.
6. The method of making a composite flexible graphite plate of claim 1, wherein the carbon microspheres are micron-sized carbon microspheres.
7. The method for preparing a composite flexible graphite plate according to claim 1, wherein in the step of alternately laminating the porous graphite paper and the conductive paste to obtain a conductive paste/porous graphite paper laminate, the number of layers of the porous graphite paper is 4-8.
8. The method of manufacturing a composite flexible graphite plate according to claim 1, wherein the mass ratio of the electroconductive paste to the porous graphite paper in the step of alternately laminating the porous graphite paper and the electroconductive paste to obtain an electroconductive paste/porous graphite paper laminate is 50% to 150%.
9. A composite flexible graphite plate manufactured by the method of manufacturing a composite flexible graphite plate according to any one of claims 1 to 8.
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| CN101101994A (en) * | 2007-07-17 | 2008-01-09 | 武汉理工大学 | Expansion graphite base compound material dual-pole board and its making method |
| CN101308924A (en) * | 2007-05-18 | 2008-11-19 | 中国科学院大连化学物理研究所 | Flexibility enhanced bipolar plate for liquid energy-storing battery and manufacture thereof |
| TW201334978A (en) * | 2012-02-23 | 2013-09-01 | Chung Shan Inst Of Science | The strengthening method of flexible graphite composite |
| CN105406092A (en) * | 2015-11-04 | 2016-03-16 | 四川大学 | Composite material for bipolar plate of fuel cell and preparation method of composite material |
| CN107819137A (en) * | 2016-09-12 | 2018-03-20 | 中国科学院金属研究所 | A kind of soft graphite bipolar plates and preparation method thereof |
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2020
- 2020-01-13 CN CN202010031589.7A patent/CN113113627A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101308924A (en) * | 2007-05-18 | 2008-11-19 | 中国科学院大连化学物理研究所 | Flexibility enhanced bipolar plate for liquid energy-storing battery and manufacture thereof |
| CN101101994A (en) * | 2007-07-17 | 2008-01-09 | 武汉理工大学 | Expansion graphite base compound material dual-pole board and its making method |
| TW201334978A (en) * | 2012-02-23 | 2013-09-01 | Chung Shan Inst Of Science | The strengthening method of flexible graphite composite |
| CN105406092A (en) * | 2015-11-04 | 2016-03-16 | 四川大学 | Composite material for bipolar plate of fuel cell and preparation method of composite material |
| CN107819137A (en) * | 2016-09-12 | 2018-03-20 | 中国科学院金属研究所 | A kind of soft graphite bipolar plates and preparation method thereof |
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