CN102569834A - High-intensity flexible graphite double-pole plate and preparation method thereof - Google Patents
High-intensity flexible graphite double-pole plate and preparation method thereof Download PDFInfo
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- CN102569834A CN102569834A CN2010105993775A CN201010599377A CN102569834A CN 102569834 A CN102569834 A CN 102569834A CN 2010105993775 A CN2010105993775 A CN 2010105993775A CN 201010599377 A CN201010599377 A CN 201010599377A CN 102569834 A CN102569834 A CN 102569834A
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- pole plate
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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
Abstract
The invention relates to a high-intensity flexible graphite fuel cell double-pole plate and a preparation method thereof, and belongs to the technical field of double-pole plate material for fuel cells. The high-intensity flexible graphite fuel cell double-pole plate is characterized in that the entire double-pole plate consists of a graphite worm and phenolic resin. The specific preparation method comprises the steps that the graphite worm is filled in a die, and the double-pole plate can be directly formed or formed by steps through adopting a mould pressing or rolling method, and the forming pressure is 30 to 100 MPa. In the prepared double-pole plate of the fuel cell, the density is 1.2 to 1.7 g/cm<3>, the thickness is 1.0 to 3.0mm, the tensile strength of the directly-formed double-pole plate combining the graphite worm and the phenolic resin is 6 to 15 MPa, the tensile strength of the double-pole plate subjected to impregnation treatment is 20 to 30 MPa, and the double-pole plate subjected to the impregnation treatment has the advantages of corrosion resistance, no reaction with electrodes or electrolytes, light weight, low thickness, excellent electric conductivity and thermal conductivity as well as excellent air permeability, simple preparation technology and low cost.
Description
Technical field
The present invention relates to compound fuel battery double plates of a kind of pure flexible graphite and phenolic resins and preparation method thereof.Belong to fuel battery double plates material and manufacturing technology field.
Background technology
The bipolar plates of Proton Exchange Membrane Fuel Cells (PEMFC), DMFC (DMFC) (Bipolar Plates); Also claim collector plate; Play a part to separate oxidant and reducing agent; And the even flow field of reactant through the plate face be assigned to electrode everywhere, carry out electrochemical reaction with electrode catalyst layer.
Therefore, in order effectively to separate oxidant and reducing agent, bipolar plates requires to have good choke function; Bipolar plates has the afflux effect, and requiring bipolar plates must be the good conductor of electricity; Guarantee battery in when work uniformity of temperature profile and the used heat of battery is got rid of smoothly, bipolar plates must be the good conductor of heat; And bipolar plates must have very strong resistance to corrosion, because fuel-cell electrolyte is an acid condition; Simultaneously, the bipolar plates both sides should process or be equipped with and make the equally distributed passage of reacting gas (being so-called flow field), and guaranteeing reaction gas in entire electrode even distribution everywhere, so bipolar plates should have good processing properties and mechanical performance; In order to improve volume of battery power and quality power, bipolar plates should have also that density is little, light weight, advantage that volume is little.Like this, be corrosion-resistant as the basic demand of Proton Exchange Membrane Fuel Cells, DMFC bipolar plates, conduct electricity very well, air penetrability is low, and is in light weight.
The material that present bipolar plates mainly adopts has metal material, impermeable graphite (Delanium), charcoal-carbon composite.
The bipolar plates conduction and the corrosion resistance that adopt Delanium to make are all good.Shortcoming is that the production process of Delanium is complicated and strict, during the consumption expenses of labour.And, because artificial stone mill is crisp, therefore require the thickness of bipolar plates bigger, be generally about 3mm, be unfavorable for the raising of battery volumetric specific power, make the flow field processing difficulties simultaneously, cost is high, is unfavorable for commercially producing in batches.Delanium is used in fuel battery performance test and fuel cell studies more at present.
The bipolar plates that metal material is made, thickness is little (generally can be reached 0.1～0.5mm), help the raising of volumetric specific power; Can adopt mechanized method for making processing duct and flow fields such as punching press punching, processing cost is low, method is simple, is suitable for commercialization and produces in enormous quantities.But the metal material bipolar plates is through the long-term corrosion-vulnerable of using, and the corrosion back produces oxide-film, causes conductance to reduce, and therefore must solve the etching problem of metallic plate.At present, many employings is metal surface modification.Through modification, not only can prevent the generation of slight corrosion, and can make contact resistance keep constant, do not increase in time.Like patent US6,426,161 have introduced and utilize magnesium, aluminium to make fuel battery double plates, and proposed utilization plating, electrochemical deposition or other method in the metal surface built up membrane, like metal-polytetrafluoroethylene; Patent US5,776,624 have introduced and utilize brass to prepare dual polar plates of proton exchange membrane fuel cell, and propose bipolar plates and which floor be made up of, and the surface is a kind of alloy, contains nickel, chromium, titanium; Patent WO2001/28020-A1 proposes plating (PVD) Ti in the metal surface
xAl
yN corrosion-resistant conductive coating, and prepare fuel battery double plates with amorphous graphite sealing of hole.Utilize flexible graphite paper to make the metal material bipolar plates in addition with the corrosion resistant plate mold pressing.In a word, its main purpose is the corrosion resistance that strengthens metallic plate, but these diaphragms can influence the conductivity of metal and cost of bipolar plates is improved greatly.Therefore, metal material is made the research that Proton Exchange Membrane Fuel Cells, DMFC bipolar plates also need go deep into.
In recent years, also developed a series of charcoal class bipolar plate materials both at home and abroad, like patent US6,248,467-B1 proposes mold pressing vinylite+powdered graphite and makes the PEMFC bipolar plates; Patent CN1282349 has proposed to make composite material double pole plate with 10～30wt% low viscosity thermosetting resin and the mold pressing of 70～90wt% conduction aggregate; Patent EP1192032-A1 proposes to prepare fuel battery double plates with expanded graphite and thermoplastic resin; Also have patent to propose to improve the admant ink material, the flow field is processed easily, and adopt quick molding methods such as mold pressing, injection moulding, perhaps use method of graphite-filled polymer or the like with resin impregnation.These bipolar plates adopt charcoal and resin to make basis material more, utilize injection moulding, hot press molding method, can reduce the manufacturing cost of bipolar plates greatly, but its electric conductivity, bipolar plates thickness, weight aspect are not very desirable.
Flexible graphite has required corrosion-resistant of bipolar plates, conduction, good heat conductivity, and principal advantages such as density is low, there therefore have patent to propose flexible graphite to be compound with resin or metallic plate, but the one side cost is higher, still can occur the bad problem of conductance on the other hand.
Summary of the invention
Be to solve the problem that exists in the prior art, the objective of the invention is to propose a kind of corrosion-resistant, flexible graphite bipolar plates that conduction, good heat conductivity and preparation technology are simple, cost is low and preparation method thereof.
A kind of high-strength flexible graphite bi-polar plate that the present invention proposes, it is characterized in that: it mainly contains expanded graphite worm and additive, and phosphorus content is not less than 99wt% in the said graphite worm.
In above-mentioned flexible graphite bipolar plates, said expanded graphite worm is with the preparation of electrochemical process intercalation scale, and also available existing method prepares expanded graphite, and at 900～1000 ℃ of following expanded preparation expanded graphite worms.
The preparation method of a kind of flexible graphite bipolar plates that the present invention proposes, it is characterized in that: said method is carried out successively as follows:
(1) graphite worm is inserted in the mould straight forming under 30～100MPa pressure, a step formation flow field and inlet, outlet, water hole;
(2) use the resin impregnating bipolar plates, and heat-treated 1～2 hour at 100～200 ℃.
In above-mentioned preparation method; Step (1) can adopt the multistep molding method; Promptly earlier graphite worm is inserted in the mould flat board about 10～20MPa forming under the pressure flexible graphite dull and stereotyped, is put into then after core rod and the oven dry; In 30～100MPa forming under the pressure bipolar plates, directly form flow field and inlet, outlet, water hole.
Utilizing the fuel battery double plates density of method preparation of the present invention is 1.5～1.8g/cm
3, thickness is 1.0～3.0mm.The pure graphite worm bipolar plates tensile strength of straight forming is 6～15MPa, and the bipolar plates intensity of process impregnation process is 20～30MPa.Bipolar plates behind the dipping has corrosion-resistant, do not have an effect with electrode, electrolyte, in light weight, thickness is little, conduction, good heat conductivity, air tight performance is good, and preparation technology is simple, low cost and other advantages.
Embodiment
Below in conjunction with embodiment the present invention is further specified:
Embodiment 1
1) expanded graphite worm is inserted in the mould, put into upper and lower core rod, straight forming bipolar plates under 40 ± 10MPa pressure;
2) impregnated phenolic resin, 150 ℃ of heat treatment 2 hours;
3) gained bipolar plates thickness is 1.0～3.0mm, and density is 1.2～1.5g/cm
3, conductance is 1.0 * 10
4S/m～1.0 * 10
5S/m, thermal conductivity is greater than 90W/mk.
Embodiment 2
1) expanded graphite worm is inserted in the mould, dull and stereotyped at 10～20MPa forming under the pressure flexible graphite;
2) put into core rod and flat board up and down, under 80 ± 10MPa pressure, the moulding bipolar plates;
3) surfaces coated 502 glue, 100 ℃ of heat treatment 1 hour;
4) gained bipolar plates thickness is 1.0～3.0mm, and density is 1.5～1.7g/cm
3, conductance is 1.0 * 10
4S/m～1.0 * 10
5S/m, thermal conductivity is greater than 100W/mk.
Embodiment 3
1) the expansible graphite half an hour of utilizing 120 ℃ of electrochemical intercalation to obtain;
2) expanded preparation expanded graphite worm under 900～1000 ℃;
3) expanded graphite worm is inserted in the mould, dull and stereotyped at 15MPa forming under the pressure flexible graphite;
4) impregnated phenolic resin, 200 ℃ of heat treatment 2 hours;
5) put into core rod and flat board up and down, under 50 ± 10MPa pressure, the moulding bipolar plates;
6) gained bipolar plates thickness is 1.0～3.0mm, and density is 1.2～1.6g/cm
3, conductance is greater than 1.0 * 10
4S/m, thermal conductivity is greater than 80W/mk.
Embodiment 4
1) expanded graphite worm is inserted in the mould, dull and stereotyped at 10～20MPa forming under the pressure flexible graphite;
2) take out flat board, and flat board is put into 120 ℃, flood half an hour in the 10wt% BAS;
3) put into core rod and flat board up and down, in 60 ± 10MPa forming under the pressure bipolar plates;
4) impregnated phenolic resin, 120 ℃ of heat treatment 2 hours;
5) gained bipolar plates thickness is 1.0～3.0mm, and density is 1.3～1.6g/cm
3, conductance is greater than 1.0 * 10
4S/m, thermal conductivity is greater than 80W/mk.
Embodiment 5
1) expanded graphite worm is inserted in the mould, dull and stereotyped at 10～20MPa forming under the pressure flexible graphite;
2) put into core rod up and down, in 70 ± 10MPa forming under the pressure bipolar plates;
3) impregnated phenolic resin, 180 ℃ of heat treatment 2 hours;
4) gained bipolar plates thickness is 1.0～3.0mm, and density is 1.5～1.7g/cm
3, conductance is greater than 1.0 * 10
4S/m, thermal conductivity is greater than 80W/mk.
Claims (3)
1. high-strength flexible graphite bi-polar plate, it is characterized in that: it mainly contains expanded graphite worm and phenolic resins, and phosphorus content is not less than 99wt% in the said graphite worm; Said expanded graphite worm prepares with electrochemical process intercalation scale, or prepares expanded graphite with existing method, and at 900～1000 ℃ of following expanded preparation expanded graphite worms.
2. the preparation method of a high-strength flexible graphite bi-polar plate, it is characterized in that: said method is carried out successively as follows:
(1) graphite worm is inserted in the mould straight forming under 30～100MPa pressure, a step formation flow field and inlet, outlet, water hole;
(2) using concentration is the resin impregnating bipolar plates of 5～20wt%, and heat-treats 1～2 hour at 100～200 ℃.
3. according to the preparation method of the described a kind of high-strength flexible graphite bi-polar plate of claim 2; It is characterized in that: step (1) adopts the multistep molding method; Promptly earlier graphite worm is inserted in the mould flat board about 10～20MPa forming under the pressure flexible graphite dull and stereotyped, is put into then after core rod and the oven dry; In 30～100MPa forming under the pressure bipolar plates, directly form flow field and inlet, outlet, water hole.
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| CN2010105993775A CN102569834A (en) | 2010-12-22 | 2010-12-22 | High-intensity flexible graphite double-pole plate and preparation method thereof |
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| CN2010105993775A CN102569834A (en) | 2010-12-22 | 2010-12-22 | High-intensity flexible graphite double-pole plate and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106876724A (en) * | 2015-12-10 | 2017-06-20 | 上海神力科技有限公司 | A kind of fuel cell rolling production method of soft graphite unipolar plate |
| CN108666585A (en) * | 2017-03-28 | 2018-10-16 | 北京亿华通科技股份有限公司 | The pole plate production method of fuel cell |
| CN109768296A (en) * | 2019-01-26 | 2019-05-17 | 杭州德海艾科能源科技有限公司 | A kind of bipolar plate of all-vanadium redox flow battery and its preparation process |
| CN109786778A (en) * | 2019-01-28 | 2019-05-21 | 威海南海碳材料科技研究院有限公司 | A kind of composite dual-electrode plates used for all-vanadium redox flow battery and preparation method thereof |
| CN109921052A (en) * | 2019-03-19 | 2019-06-21 | 上海神力科技有限公司 | A kind of preparation method of vertical lamellar structure flexible graphite polar plate |
| CN109950569A (en) * | 2019-04-01 | 2019-06-28 | 清华大学 | A kind of molding preparation method of fuel battery double plates |
| CN111129537A (en) * | 2019-12-31 | 2020-05-08 | 一汽解放汽车有限公司 | Composite graphite bipolar plate and preparation method and application thereof |
| CN111916782A (en) * | 2020-06-29 | 2020-11-10 | 惠州市杜科新材料有限公司 | Ultrathin graphite composite bipolar plate base material capable of being rapidly cold-pressed and formed and preparation method thereof |
| CN112490460A (en) * | 2020-11-16 | 2021-03-12 | 广东国鸿氢能科技有限公司 | Injection-molded graphite bipolar plate and preparation method thereof |
| CN114824342A (en) * | 2021-01-28 | 2022-07-29 | 上海神力科技有限公司 | Preparation method of graphite polar plate, fuel cell and vehicle |
| CN115322516A (en) * | 2022-08-18 | 2022-11-11 | 厦门泰启力飞科技有限公司 | High-performance fuel cell bipolar plate base material and preparation method thereof |
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| US20020064702A1 (en) * | 1998-12-30 | 2002-05-30 | Gibb Peter R. | Fuel cell fluid flow field plate and methods of making fuel cell flow field plates |
| CN1719645A (en) * | 2004-07-06 | 2006-01-11 | 中国科学院大连化学物理研究所 | A kind of bipolar board for new proton exchange film fuel battery preparation technology |
| 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 |
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2010
- 2010-12-22 CN CN2010105993775A patent/CN102569834A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20020064702A1 (en) * | 1998-12-30 | 2002-05-30 | Gibb Peter R. | Fuel cell fluid flow field plate and methods of making fuel cell flow field plates |
| CN1719645A (en) * | 2004-07-06 | 2006-01-11 | 中国科学院大连化学物理研究所 | A kind of bipolar board for new proton exchange film fuel battery preparation technology |
| 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 |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106876724A (en) * | 2015-12-10 | 2017-06-20 | 上海神力科技有限公司 | A kind of fuel cell rolling production method of soft graphite unipolar plate |
| CN108666585A (en) * | 2017-03-28 | 2018-10-16 | 北京亿华通科技股份有限公司 | The pole plate production method of fuel cell |
| CN109768296B (en) * | 2019-01-26 | 2020-08-07 | 杭州德海艾科能源科技有限公司 | Full-vanadium redox flow battery bipolar plate and preparation process thereof |
| CN109768296A (en) * | 2019-01-26 | 2019-05-17 | 杭州德海艾科能源科技有限公司 | A kind of bipolar plate of all-vanadium redox flow battery and its preparation process |
| CN109786778A (en) * | 2019-01-28 | 2019-05-21 | 威海南海碳材料科技研究院有限公司 | A kind of composite dual-electrode plates used for all-vanadium redox flow battery and preparation method thereof |
| CN109921052A (en) * | 2019-03-19 | 2019-06-21 | 上海神力科技有限公司 | A kind of preparation method of vertical lamellar structure flexible graphite polar plate |
| CN109950569B (en) * | 2019-04-01 | 2021-01-08 | 清华大学 | Die pressing preparation method of fuel cell bipolar plate |
| CN109950569A (en) * | 2019-04-01 | 2019-06-28 | 清华大学 | A kind of molding preparation method of fuel battery double plates |
| CN111129537A (en) * | 2019-12-31 | 2020-05-08 | 一汽解放汽车有限公司 | Composite graphite bipolar plate and preparation method and application thereof |
| CN111916782A (en) * | 2020-06-29 | 2020-11-10 | 惠州市杜科新材料有限公司 | Ultrathin graphite composite bipolar plate base material capable of being rapidly cold-pressed and formed and preparation method thereof |
| CN112490460A (en) * | 2020-11-16 | 2021-03-12 | 广东国鸿氢能科技有限公司 | Injection-molded graphite bipolar plate and preparation method thereof |
| CN114824342A (en) * | 2021-01-28 | 2022-07-29 | 上海神力科技有限公司 | Preparation method of graphite polar plate, fuel cell and vehicle |
| CN115322516A (en) * | 2022-08-18 | 2022-11-11 | 厦门泰启力飞科技有限公司 | High-performance fuel cell bipolar plate base material and preparation method thereof |
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Application publication date: 20120711 |