CN101246964B - Stainless steel double-polar plate surface modifying method for proton exchange film fuel battery - Google Patents
Stainless steel double-polar plate surface modifying method for proton exchange film fuel battery Download PDFInfo
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- CN101246964B CN101246964B CN2008100332887A CN200810033288A CN101246964B CN 101246964 B CN101246964 B CN 101246964B CN 2008100332887 A CN2008100332887 A CN 2008100332887A CN 200810033288 A CN200810033288 A CN 200810033288A CN 101246964 B CN101246964 B CN 101246964B
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- stainless steel
- proton exchange
- bipolar plate
- exchange membrane
- fuel cell
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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 present invention provides a surface modification method of stainless steel bipolar plate of proton exchange membrane fuel cell belonged to field of energy source. Injecting nickel ion to stainless steel plate by ion injection method, forming injection layer at range of several decade nanometer on surface of stainless plate, and modified stainless steel bipolar plate is obtained. The present invention can improve corrosion resistance, reduce contact resistance of metal bipolar plate and gas diffusion layer to meet the acquirement of development of proton exchange membrane fuel cell.
Description
Technical field
The present invention relates to the preparation method's in a kind of fuel cell technology field, particularly a kind of proton exchange membrane fuel cell stainless steel bipolar plate surface modifying method.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is to be electrolyte with perfluorinated sulfonic acid type solid polymer, platinum/carbon or platinum-ruthenium/carbon is eelctro-catalyst, hydrogen or purification reformation gas are fuel, air or pure oxygen are oxidant, and working temperature generally is converted into the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy at 60～100 ℃ the chemical energy with in fuel and the oxidant.Under the situation serious day by day in global environmental pollution, that fossil energy is exhausted day by day, have advantages such as efficient, energy-conservation, safety, environmental protection because of it and enjoy national governments and research organizations pay much.Along with the application of PEMFC in the vehicles such as automobile, it can be penetrated into social all trades and professions and even average family gradually as energy technology of new generation, the application prospect that it is wide even can compare favourably with computer technology.But the too high cost of PEMFC limits it and applies on a large scale.As the bipolar plates of one of PEMFC critical component, not only occupy the 70%-80% of pile weight, and in the production cost of pile, also occupy sizable ratio.
The function of bipolar plates is collected current and its anode from a battery is transmitted to the negative electrode of next battery, distributes fuel gas equably at anode surface simultaneously, in cathode surface uniform distribution oxygen/air.In addition, it also must have cooling fluid to pass through the passage of pile and guarantee that cold fluid separates with reactant gas.The graphite-like bipolar plates that conduction is good, be easy to process the flow field is that the commercialization process of PEMFC has been established good start, also be the plate material that PEMFC extensively adopts, but its bad mechanical strength, processing cost height make it lack enough competitiveness in the industrial applications of PEMFC.Composite graphite plate, flexible graphite and sheet metal plate all are very potential bipolar plates alternate materials, and the sheet metal bipolar plates not only is easy to realize producing in batches, reducing the pile cost, can increase substantially the pile specific power, be the most competitive plate material.The great advantage of metal double polar plates is to be easy to a large amount of generate and thickness can reduce significantly that (100～300um), the specific energy of battery pile and specific power also can therefore and significantly improve.Yet, the both sides of PEMFC bipolar plates are respectively wet oxidant and wet reducing agent, the glassware for drinking water that can oligodynamical electrochemical reaction is generated owing to gas ions has faint acidity, with the common metal material during as bipolar plates, slight corrosion can take place and causes the activity of electrode catalyst to reduce.Therefore, the PEMFC metal double polar plates can adopt some decay resistances own just to carry out modification than more excellent alloy system as the metal bipolar panel material or at the unfavorable alloy surface of corrosion resistance.Gold plate and nickel plate are owing to its excellent decay resistance and low surface contacted resistance are used to the metal double polar plates of Proton Exchange Membrane Fuel Cells, and be too high but its shortcoming is a cost, commercially produced very big difficulty.
Find through the literature search to prior art; (H.Wang et al.)＜＜Journal of PowerSources (energy magazine) (138 phase 79-85 pages or leaves in 2004) deliver (" Thermallynitrided stainless steel for polymer electrolyte membrane fuel cellbipolar plate Part 2:Beneficial modification of passive layer on AISI446 ") (thermal nitridation stainless steel as Proton Exchange Membrane Fuel Cells 2: to the useful modification of AISI446 passivation film on stainless steel surface) points out can significantly improve stainless decay resistance in 2 hours 1100 ℃ of nitridings, produces thermal deformation but its weak point is that too high temperature can make through stamping forming bipolar plate of stainless steel.
In sum, the two hang-ups-corrosion resistance used of metal double polar plates and conductivity-still need to be resolved hurrily.Therefore, develop and a kind ofly can improve the corrosion resistance of metal double polar plates under fuel cell environment, do not influence the method for modifying of its electric conductivity again, seem very necessary to reducing cost of bipolar plates and prolonging its useful life, the commercialization process of Proton Exchange Membrane Fuel Cells is had important and practical meanings.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, the surface modifying method of one metal double-plate for proton exchange film fuel cell is provided, make the contact resistance of its decay resistance that can further improve metal double polar plates, reduction metal double polar plates and gas diffusion layers (carbon paper), to satisfy the demand for development of Proton Exchange Membrane Fuel Cells.
The present invention is achieved by the following technical solutions, and the method that the present invention adopts ion to inject is injected stainless sheet steel with nickel ion, forms implanted layer in tens nanometer range of stainless sheet steel surface, obtains the bipolar plate of stainless steel after the modification.Because implanted layer is for reducing surface contacted resistance and improving corrosion proof rich nickel dam, so the bipolar plate of stainless steel corrosion resistance after the modification improves and contact resistance reduces.
Described ion injects, and its accelerating voltage is 20KeV～60KeV, and beam intensity is 4uA～8uA.
Described ion injects, and its vacuum degree is 110
-3Pa～3 * 10
-3Pa.
Described nickel ion, its implantation dosage scope is 5 * 10
16～5 * 10
17Ions/cm
2
Described implanted layer, its thickness are 50nm～100nm.
Described stainless sheet steel, its thickness are 0.1mm～0.2mm.
Described stainless sheet steel carries out oil removing, dried before ion injects.
The present invention compares with existing method, have following advantage and characteristic: the present invention adopts ion implantation technique, the bipolar plate surfaces temperature has been compared with other technologies significantly and has been reduced during injection, it only is 100 ℃～200 ℃, can effectively prevent corrosion resistant plate thermoresilience, thereby greatly reduce the unevenness of corrosion resistant plate through the punching press distortion; And can form corrosion resistance anticorrosion layer preferably at stainless steel surfaces, and stainless corrosion potential is brought up to-0.05V from-0.3V, passivation current density is reduced to 7 microamperes every square centimeter by 12 microamperes every square centimeter in cathode environment; Greatly reduce the material cost of bipolar plates with respect to other Langaloy plates and nickel plate; High reduction the surface contacted resistance between stainless steel and the carbon paper, under every square centimeter of 150 newton's thrust, from 402.75 milliohm square centimeters to 67.5 milliohm square centimeters; Can make thin metal double polar plates, improve specific energy and the volumetric specific energy of PEMFC, thereby reduce the cost of Proton Exchange Membrane Fuel Cells, promote its further promotion and application.
Description of drawings
Fig. 1 is the 316L stainless steel and injects the stainless steel of nickel and the pressure-dependent schematic diagram of contact resistance of carbon paper through ion.
Fig. 2 is 316L stainless steel and the polarization curve schematic diagram of the stainless steel that injects nickel through ion under the simulation anode-context.
Fig. 3 is 316L stainless steel and the polarization curve schematic diagram of the stainless steel that injects nickel through ion under the simulation cathode environment.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
As shown in Figure 1, be the 316L stainless steel and inject the stainless steel of nickel and the pressure-dependent schematic diagram of contact resistance of carbon paper through ion.Among the figure, abscissa is a pressure, and unit is newton/square centimeter; Ordinate is a surface contacted resistance, and unit is the milliohm square centimeter; Black square ■ represents the original material bipolar plates, and all the other represent the 316L corrosion resistant plate of embodiment 1～embodiment 5 after ion injects nickel respectively.
Fig. 2,3 is respectively 316L stainless steel and the polarization curve schematic diagram of stainless steel under simulation anode and cathode environment that injects nickel through ion.Abscissa is an electromotive force among Fig. 2,3, and unit is a volt, and reference electrode is a saturated calomel electrode; Ordinate is a current density, and unit is an ampere/square centimeter; Black curve is represented the 316L corrosion resistant plate, and all the other represent the 316L corrosion resistant plate of embodiment 1～embodiment 5 after ion injects nickel respectively.Get the square that the 316L stainless steel is cut into 15cm * 15cm, wash, after degreasing dries up, put into the multifunction ion coating machine and vacuumize, treat that vacuum degree arrives 1～3 * 10 through routine polishing, washing, alcohol
-3Begin ion during Pa and inject nickel, accelerating voltage is 20～60KeV during injection, and beam intensity is 4～8uA.The contact resistance of bipolar plate of stainless steel after the modification and gas diffusion layers (carbon paper) and the relation of pressure are seen Fig. 1.At fuel cell simulation anode and cathode environment (0.5mol/L H
2SO
4+ 2ppmHF solution, 80 ℃, logical respectively hydrogen and oxygen) in polarization curve see Fig. 2, Fig. 3.As seen from the figure, behind ion injection nickel, the contact resistance of stainless steel and carbon paper reduces and decay resistance improves a lot.To inject nickel was example in 1 hour, at 180N/cm
2Pressure under, the contact resistance of 316L stainless steel and carbon paper is 351m Ω cm
2, and after ion injects nickel, be 54m Ω cm
2In the simulation anode-context, the stainless corrosion potential of 316L be-0.3V, brings up to-0.02V through ion injection corrosion potential, and the work potential that is higher than the Proton Exchange Membrane Fuel Cells anode (0.1V), illustrates that it exempts to lose in anode-context.In the simulation cathode environment, the stainless current density of 316L is 11.26 μ A/cm
2, be reduced to 7.91 μ A/cm through its current density behind the ion injection nickel
2Concrete technological parameter sees the following form:
The bipolar plate of stainless steel that table 1 different technology conditions is handled
| Embodiment | Matrix | Inject energy (keV) | Implantation dosage (ions/cm 2) | Contact resistance | Corrosion resistance |
| Ni?1 | The 316L stainless steel | 20 | 5×10 16ions/cm 2 | Well | Better |
| Ni?2 | The 316L stainless steel | 30 | 1×10 17ions/cm 2 | Well | Well |
| Ni?3 | The 316L stainless steel | 40 | 2×10 17ions/cm 2 | Well | Well |
| Ni?4 | The 316L stainless steel | 50 | 3×10 17ions/cm 2 | Better | Well |
| Ni?5 | The 316L |
60 | 5×10 17ions/cm 2 | Better | Better |
Claims (6)
1. the surface modifying method of a proton exchange membrane fuel cell stainless steel bipolar plate, it is characterized in that, the method that adopts ion to inject is injected stainless sheet steel with nickel ion, forms implanted layer in tens nanometer range of stainless sheet steel surface, obtains the bipolar plate of stainless steel after the modification;
Described implanted layer, its thickness are 50nm～100nm.
2. the surface modifying method of proton exchange membrane fuel cell stainless steel bipolar plate according to claim 1 is characterized in that, described ion injects, and its accelerating voltage is 20KeV～60KeV, and beam intensity is 4uA～8uA.
3. the surface modifying method of proton exchange membrane fuel cell stainless steel bipolar plate according to claim 1 and 2 is characterized in that, described ion injects, and its vacuum degree is 1 * 10
-3Pa～3 * 10
-3Pa.
4. the surface modifying method of proton exchange membrane fuel cell stainless steel bipolar plate according to claim 1 is characterized in that, described nickel ion, and its implantation dosage scope is 5 * 10
16～5 * 10
17Ions/cm
2
5. the surface modifying method of proton exchange membrane fuel cell stainless steel bipolar plate according to claim 1 is characterized in that, described stainless sheet steel, its thickness are 0.1mm～0.2mm.
6. the surface modifying method of proton exchange membrane fuel cell stainless steel bipolar plate according to claim 1 is characterized in that, described stainless sheet steel carries out oil removing, dried before ion injects.
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| CN2008100332887A CN101246964B (en) | 2008-01-31 | 2008-01-31 | Stainless steel double-polar plate surface modifying method for proton exchange film fuel battery |
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|---|---|---|---|
| CN2008100332887A CN101246964B (en) | 2008-01-31 | 2008-01-31 | Stainless steel double-polar plate surface modifying method for proton exchange film fuel battery |
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| CN101246964B true CN101246964B (en) | 2011-08-31 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670990A (en) * | 2004-03-19 | 2005-09-21 | 三星Sdi株式会社 | Metallic separator for fuel cell and method for anti-corrosion treatment of the same |
| CN101032047A (en) * | 2005-02-01 | 2007-09-05 | 株式会社新王材料 | Separator for fuel cell and method for manufacturing same |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670990A (en) * | 2004-03-19 | 2005-09-21 | 三星Sdi株式会社 | Metallic separator for fuel cell and method for anti-corrosion treatment of the same |
| CN101032047A (en) * | 2005-02-01 | 2007-09-05 | 株式会社新王材料 | Separator for fuel cell and method for manufacturing same |
| 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 |
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