CN102005580B - Surface-modifying treatment method of stainless steel bipolar plate of proton exchange membrane fuel cell - Google Patents
Surface-modifying treatment method of stainless steel bipolar plate of proton exchange membrane fuel cell Download PDFInfo
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- CN102005580B CN102005580B CN2010105310523A CN201010531052A CN102005580B CN 102005580 B CN102005580 B CN 102005580B CN 2010105310523 A CN2010105310523 A CN 2010105310523A CN 201010531052 A CN201010531052 A CN 201010531052A CN 102005580 B CN102005580 B CN 102005580B
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- ionic liquid
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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 discloses a surface-modifying treatment method of a stainless steel bipolar plate of a proton exchange membrane fuel cell, comprising the steps of taking two electrode bodies in an ion liquid and depositing a proper amount of metal niobium on the surface of the stainless steel bipolar plate, wherein the method for depositing the metal niobium comprises the following steps of: reducing NbCl5 dissolved in diethyl ether into Nb3Cl8 with aluminum powder; transferring the prepared solution to 1-ethyl-3-methyl sulfonated trifluoro mesylate rescriptor salt liquid containing a proper percent by weight of sodium chloride into an ion liquid; and depositing the metal niobium to the surface of the stainless steel bipolar plate in the ion liquid by taking the stainless steel bipolar plate as a cathode and a pure niobium plate as an anode. The invention has the benefits that the corrosion resistant performance of the stainless steel bipolar plate is remarkably improved; the polar plate has enough mechanical strength; the modification process is simple and the processing cost is low; the invention has important practical significance on the acceleration of commercialized progress; and the used deposition liquid cannot cause the pollution.
Description
Technical field
The present invention relates to the Proton Exchange Membrane Fuel Cells field, relate in particular to proton exchange membrane fuel cell stainless steel bipolar plate, be specifically related to the stainless steel double-polar plate surface modifying processing method.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) be take perfluorinated sulfonic acid type solid polymer as electrolyte, hydrogen or purify reformed gas as fuel, air or oxygen as oxidant, the chemical energy in fuel and the oxidant is converted into the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy.Bipolar plates is one of fuel cell critical component, and it generally comprises pole plate and flow field.Pole plate major function in fuel cell is: 1) collected current, thereby must be the good conductor of electricity; 2) guaranteeing that battery temperature is evenly distributed and the enforcement of heat sink conception, must be the good conductor of heat; 3) sheet resistance is low, reduces the internal resistance of cell; 4) have certain mechanical strength and rigidity, creep does not occur under battery-operated environment; 5) fuel and oxidant non-penetrative can be separated oxidant and reducing agent; 6) corrosion-resistant in the battery electrochemical environment; 7) low-density is with the specific power density that improves battery etc.The flow field then is uniform distribution fuel and oxidant, guarantees that electric current distribution is even, avoids local overheating, and makes reaction end gas can discharge battery generation water.
In Proton Exchange Membrane Fuel Cells (PEMFC), bipolar plates not only occupies the major part of volume and weight, and occupies the sizable ratio of production cost, becomes to hinder one of business-like critical component of Proton Exchange Membrane Fuel Cells.Traditional Proton Exchange Membrane Fuel Cells (PEMFC) bipolar plates is carbon slab, and carbon slab fragility is large, bad mechanical strength, and processing cost is all relatively more expensive.Metallic plate not only has enough mechanical strengths, and is easy to machine-shaping and batch production, is most potential carbon plate substitution material.But undressed metallic plate easy corrosion under battery context, and the metal ion that corrosion forms deposits in proton exchange membrane reduces the proton handling capacity and has a strong impact on battery performance, thereby metallic plate must carry out modification.In the prior art, Fronk Matthew Howard et al (US6372376) has proposed to apply on aluminium, the titanium matrix method of composite conducting layer (raw material of wood-charcoal or conducting polymer+non-soluble polymer), although the method operates more convenient, the problem of stress concentration of composite conducting layer is difficult for solving after the raising conductivity.Other has had patent report the aluminium both sides has been covered the method for modifying of conducting polymer, for strengthening the adhesion of matrix and conducting polymer, must carry out mechanical treatment to the aluminium surface.Wang Yu newly waits (CN01144972) to disclose processing method in the attached sheet metal of graphite worm layer therebetween or polypyrrole or polyaniline network layer, the method is characterized in that to place behind the metallic plate after pressure forming or the graphite worm pressure forming electropolymerization polyaniline or polypyrrole in intermediate gaps in two-layer graphite worm.Because the overall structure of pole plate is graphite worm, has problems of mechanical strength.Li Moucheng etc. are in " dual polar plates of proton exchange membrane fuel cell " (China Patent No.: the method for modifying that discloses metal surface coated with conductive oxide 02155187).Zeng Xianlins etc. are in " making process of two plates of proton exchange film fuel cell " (China Patent No.: the manufacture method that has proposed the resin surface plated nickel, titanium, gold etc. of injection mo(u)lding 01118343.8).
To sum up, because carbon slab fragility is large, bad mechanical strength, processing cost is all relatively more expensive simultaneously, and there is greatly difficulty in its large-scale commercial applications application.Aluminium sheet is active especially, and very easily corrosion does not also have suitable method of modifying up to now under the PEMFC environment, and the oxide-film of titanium plate itself significantly increases internal resistance, the noble metal such as electrogilding normally, and processing cost also is difficult for acceptance during batch production.The thin layer corrosion resistant plate that is easy to machine-shaping and batch production is most potential pole plate substitution material, but there is etching problem equally in the thin layer corrosion resistant plate under the PEMFC environment.In the domestic and international disclosed document, the research of bipolar plates concentrates on precious metal plating and utilizes the multi sphere coating technique to prepare on the conductive coating.Therefore, develop and a kind ofly novel can improve the corrosion resistance of corrosion resistant plate under battery context, do not affect again the method for modifying of its electrical property, to seeming very necessary the useful life that prolongs bipolar plates, and the commercialization process of Proton Exchange Membrane Fuel Cells is had important practical significance.
Summary of the invention
The purpose of this invention is to provide a kind of method of modifying of simple proton exchange membrane fuel cell stainless steel bipolar plate, improve the corrosion resistance of bipolar plate of stainless steel in fuel cell environment.
Technical solution of the present invention is: a kind of proton exchange membrane fuel cell stainless steel bipolar plate surface modifying treatment, comprise with two electrode systems in ionic liquid, with the direct current electrode position technology to bipolar plate of stainless steel surface deposition metal, it is characterized in that: described usefulness two electrode systems are in ionic liquid, metal niobium with the direct current electrode position technology to the metal of bipolar plate of stainless steel surface deposition, described usefulness two electrode systems may further comprise the steps with the method for direct current electrode position technology to bipolar plate of stainless steel surface deposition metal niobium in ionic liquid:
A, will be dissolved in NbCl in the ether with aluminium powder
5Be reduced to Nb
3Cl
8, aluminum reduction NbCl
5In the process, aluminium powder and NbCl
5Mol ratio be 3:1～1:3;
B, the solution that a step is made are transferred in the 1-ethyl-3-methylimidazole fluoroform sulphonate liquid that contains an amount of mass fraction sodium chloride and are configured to ionic liquid, in ionic liquid, and aluminium powder, NbCl
5With 1-ethyl-3-methylimidazole fluoroform sulphonate three's ratio at 3:1:1～1:3:10; With 1-ethyl-3-methylimidazole fluoroform sulphonate level meter, the mass fraction of sodium chloride is 1%～3%;
C, take through pretreated bipolar plate of stainless steel as negative electrode, pure niobium plate is anode, in the ionic liquid that b step mule is configured to, uses the method for direct current electrode position to bipolar plate of stainless steel surface deposition metal niobium, the voltage range of direct current electrode position is 12V～29V, and electroplating time is 10 minutes～12 hours.
A kind of proton exchange membrane fuel cell stainless steel bipolar plate surface modifying treatment of the present invention; it is characterized in that described usefulness two electrode systems are in ionic liquid; place the container of logical Ar gas to the ionic liquid of the step b of the method for bipolar plate of stainless steel surface deposition metal niobium configuration with the direct current electrode position technology, under Ar gas protection of the environment to bipolar plate of stainless steel surface deposition metal niobium.
A kind of proton exchange membrane fuel cell stainless steel bipolar plate surface modifying treatment of the present invention, it is characterized in that described usefulness two electrode systems in ionic liquid, is 0.35%～8% with the direct current electrode position technology to the metal niobium content mass fraction of bipolar plate of stainless steel surface deposition.
A kind of proton exchange membrane fuel cell stainless steel bipolar plate surface modifying treatment of the present invention is characterized in that the pretreated bipolar plate of stainless steel of described process is to dry up processing through polishing, washing, alcohol wash and degreasing.
The present invention has following beneficial effect:
1, ooze the corrosion potential raising 600mV of bipolar plate of stainless steel under the simulated battery anode-context after the niobium modification through the present invention, improve 500mV in the cathode environment, corrosion resistance significantly improves.
2, the present invention is deposited on the corrosion resistant plate surface with an amount of metal niobium, and the main body of pole plate is still corrosion resistant plate, thereby pole plate still has enough mechanical strengths.
3. the present invention utilizes the direct current electrode position technology, the an amount of metal niobium of Direct precipitation is carried out modification to it on corrosion resistant plate, preparation technology is simple, and processing cost is low, to the production cost that reduces dual polar plates of proton exchange membrane fuel cell, accelerate its commercialization process and have important practical significance.
4. the deposit fluid that uses in the deposition process of the present invention is the ionic liquid of environmental protection, can not pollute.
5. the present invention is with a wide range of applications.Utilize the method for direct current electrode position in corrosion resistant plate surface Direct precipitation metal niobium, can significantly improve the corrosion resistance of corrosion resistant plate, can be mass, for being about to enter the fuel cell of commercial market, have broad application prospects.The present invention is applicable to the surface modification that low-temperature fuel cell is used bipolar plate of stainless steel, the surface modification of particularly suitable Proton Exchange Membrane Fuel Cells thin layer bipolar plate of stainless steel.
Description of drawings
The present invention has accompanying drawing two width of cloth, wherein:
Fig. 1 is at simulated battery anode-context (80 ℃ of temperature, corrosive liquid 0.5mol/L H with 304 bipolar plate of stainless steel of method modification of the present invention and 304 bipolar plate of stainless steel of not doing modification
2SO
4+ 2ppm F
-Solution, continuously logical H
2Put into sample after two hours) the polarization curve comparison diagram.
Fig. 2 is at simulated battery anode-context (80 ℃ of temperature, corrosive liquid 0.5mol/L H with 304 bipolar plate of stainless steel of method modification of the present invention and 304 bipolar plate of stainless steel of not doing modification
2SO
4+ 2ppm F
-Solution is continuously put into style behind the blowing air 30min) the polarization curve comparison diagram.
In the accompanying drawing, being polarization curve with 304 bipolar plate of stainless steel after the method modification of the present invention with the curve of round dot, is not the polarization curve of not doing 304 bipolar plate of stainless steel after the modification with the curve of round dot.
Embodiment
Commercial 304 stainless steels are made bipolar plates after routine polishing, washing, alcohol wash, degreasing dry up, aluminium powder is added be dissolved with NbCl
5Ether in, with the NbCl that is dissolved in the ether
5Be reduced to Nb
3Cl
8, aluminium powder and NbCl
5Mol ratio be 3:1～1:3; The above-mentioned solution that makes transferred in the 1-ethyl-3-methylimidazole fluoroform sulphonate liquid that contains an amount of mass fraction sodium chloride be configured to ionic liquid, take the pretreated bipolar plate of stainless steel of process as negative electrode, pure niobium plate is anode, put in advance the ionic liquid (emimOTf) that the 1-ethyl-3-methylimidazole fluoroform sulphonate liquid-mixing that contains sodium chloride of logical Ar gas is set to, the ratio of each material is in the ionic liquid: the proportional control of Al:NbCl5:emimOTf is at 1:3:10.Add 3% NaCl in the ionic liquid.The temperature of ionic liquid is controlled at 155 ° of C, and with DC power supply electro-deposition niobium, constant voltage deposition 12min under 15.9V boosts to 21.8V more first, and deposition 1h20min obtains bipolar plates after the modification after the cleaning.Bipolar plates and the bipolar plates of not doing modification are at simulated battery anode-context (80 ℃ of temperature, corrosive liquid 0.5mol/LH2SO4+2ppm F-solution, continuously logical H after the modification
2Put into style behind two hours or the air 30min) the polarization curve contrast see accompanying drawing.Polarization curve contrast demonstration, the corrosion resistance of 304 bipolar plate of stainless steel significantly improves after oozing the niobium modification.
Difference from Example 1 is:
The ratio of each material is in the ionic liquid: Al:NbCl
5: the proportional control of emimOTf is at 2.4:1:1.3, and the addition in the ionic liquid among the NaCl is 2%.The temperature of ionic liquid is controlled at 70 ° of C, and with DC power supply electro-deposition niobium, constant voltage deposition 30min under 28.7V is depressured to 19.6V more first, and deposition 10h obtains sample after the cleaning.
The result: 304 stainless steels corrosion potential in corrosion simulation liquid also significantly improves after oozing the niobium modification, and passive current density reduces, and corrosion resistance improves.
Difference from Example 2 is:
The ratio of each material is Al:NbCl in the ionic liquid
5: the proportional control of emimOTf is at 3:2:4, and the addition in the ionic liquid among the NaCl is 1%, and temperature is controlled at 130 ° of C.The constant voltage deposition 20min under 28.7V of elder generation is depressured to 18.0V again during electro-deposition, and deposition 13min obtains sample after the cleaning.
Claims (4)
1. proton exchange membrane fuel cell stainless steel bipolar plate surface modifying treatment, comprise with two electrode systems in ionic liquid, with the direct current electrode position technology to stainless steel double polar surface deposition metal, it is characterized in that: described usefulness two electrode systems are in ionic liquid, metal niobium with the direct current electrode position technology to the metal of bipolar plate of stainless steel surface deposition, described usefulness two electrode systems may further comprise the steps with the method for direct current electrode position technology to bipolar plate of stainless steel surface deposition metal niobium in ionic liquid:
A, will be dissolved in NbCl in the ether with aluminium powder
5Be reduced to Nb
3Cl
8, aluminum reduction NbCl
5In the process, aluminium powder and NbCl
5Mol ratio be 3:1～1:3;
B, the solution that a step is made are transferred in the 1-ethyl-3-methylimidazole fluoroform sulphonate liquid that contains an amount of mass fraction sodium chloride and are configured to ionic liquid, in ionic liquid, and aluminium powder, NbCl
5With 1-ethyl-3-methylimidazole fluoroform sulphonate three's ratio at 3:1:1～1:3:10; With 1-ethyl-3-methylimidazole fluoroform sulphonate level meter, the mass fraction of sodium chloride is 1%～3%;
C, take through pretreated bipolar plate of stainless steel as negative electrode, pure niobium plate is anode, in the ionic liquid that the b arrangements of steps becomes, uses the method for direct current electrode position to bipolar plate of stainless steel surface deposition metal niobium, the voltage range of direct current electrode position is 12V～29V, and electroplating time is 10 minutes～12 hours.
2. according to the described a kind of proton exchange membrane fuel cell stainless steel bipolar plate surface modifying treatment of claim 1; it is characterized in that described usefulness two electrode systems are in ionic liquid; place the container of logical Ar gas to the ionic liquid of the step b of the method for bipolar plate of stainless steel surface deposition metal niobium configuration with the direct current electrode position technology, under Ar gas protection of the environment to bipolar plate of stainless steel surface deposition metal niobium.
3. according to the described a kind of proton exchange membrane fuel cell stainless steel bipolar plate surface modifying treatment of claim 1, it is characterized in that described usefulness two electrode systems in ionic liquid, is 0.35%～8% with the direct current electrode position technology to the metal niobium content mass fraction of bipolar plate of stainless steel surface deposition.
4. according to the described a kind of proton exchange membrane fuel cell stainless steel bipolar plate surface modifying treatment of claim 1, it is characterized in that the pretreated bipolar plate of stainless steel of described process is to dry up processing through polishing, washing, alcohol wash and degreasing.
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| CN2010105310523A CN102005580B (en) | 2010-11-03 | 2010-11-03 | Surface-modifying treatment method of stainless steel bipolar plate of proton exchange membrane fuel cell |
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| CN113328110A (en) * | 2021-05-25 | 2021-08-31 | 上海电力大学 | Surface modified stainless steel bipolar plate of proton exchange membrane fuel cell and preparation method thereof |
| CN114927658B (en) * | 2022-05-06 | 2024-02-27 | 中国科学院上海硅酸盐研究所 | Device and method for modifying surface of positive electrode material based on ion exchange membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092688A (en) * | 2007-05-28 | 2007-12-26 | 大连理工大学 | Ion plating modified method for bipolar plate of stainless steel for fuel cell in type of proton exchange membrane |
| CN101222053A (en) * | 2007-12-14 | 2008-07-16 | 新源动力股份有限公司 | Stainless steel double-polar plate surface modifying method for proton exchange film fuel battery |
| CN101289755A (en) * | 2007-04-18 | 2008-10-22 | 新源动力股份有限公司 | Process for modifying surface of PEMFC stainless steel bipolar plate |
| CN101710621A (en) * | 2009-12-11 | 2010-05-19 | 江苏新源动力有限公司 | Proton exchange membrane fuel cell stainless steel bipolar plate and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8246808B2 (en) * | 2008-08-08 | 2012-08-21 | GM Global Technology Operations LLC | Selective electrochemical deposition of conductive coatings on fuel cell bipolar plates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289755A (en) * | 2007-04-18 | 2008-10-22 | 新源动力股份有限公司 | Process for modifying surface of PEMFC stainless steel bipolar plate |
| CN101092688A (en) * | 2007-05-28 | 2007-12-26 | 大连理工大学 | Ion plating modified method for bipolar plate of stainless steel for fuel cell in type of proton exchange membrane |
| CN101222053A (en) * | 2007-12-14 | 2008-07-16 | 新源动力股份有限公司 | Stainless steel double-polar plate surface modifying method for proton exchange film fuel battery |
| CN101710621A (en) * | 2009-12-11 | 2010-05-19 | 江苏新源动力有限公司 | Proton exchange membrane fuel cell stainless steel bipolar plate and method for preparing same |
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