WO2013073330A1 - 燃料電池用集電板及びその製造方法 - Google Patents

燃料電池用集電板及びその製造方法 Download PDF

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Publication number
WO2013073330A1
WO2013073330A1 PCT/JP2012/076939 JP2012076939W WO2013073330A1 WO 2013073330 A1 WO2013073330 A1 WO 2013073330A1 JP 2012076939 W JP2012076939 W JP 2012076939W WO 2013073330 A1 WO2013073330 A1 WO 2013073330A1
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Prior art keywords
plating film
collector plate
current collector
noble metal
fuel cell
Prior art date
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Ceased
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PCT/JP2012/076939
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English (en)
French (fr)
Japanese (ja)
Inventor
洋介 川村
畠沢　良之
喜弘 田口
稔啓 中川
篤史 太田
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Nippon Light Metal Co Ltd
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Nippon Light Metal Co Ltd
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Publication date
Application filed by Nippon Light Metal Co Ltd filed Critical Nippon Light Metal Co Ltd
Priority to EP12850407.3A priority Critical patent/EP2782177A4/en
Priority to US14/357,788 priority patent/US20140308602A1/en
Priority to CN201280055735.3A priority patent/CN103931034B/zh
Publication of WO2013073330A1 publication Critical patent/WO2013073330A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M8/0206—Metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • 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
    • 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
    • H01M8/0206—Metals or alloys
    • H01M8/0208—Alloys
    • 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
    • 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

Definitions

  • the present invention relates to a current collector plate for a fuel cell that is disposed at both ends of a cell stack in which a plurality of fuel cell unit cells are stacked and used to extract current, and a method for manufacturing the same.
  • an electrolyte membrane is usually sandwiched between a pair of electrodes consisting of an anode and a cathode, and a plurality of fuel cell unit cells each having a separator on each of the anode side and the cathode side are stacked, and the stacking direction of this cell stack Current collectors are taken out by providing current collecting plates at both ends of the plate.
  • the current collector plate is required to have a low contact resistance in order to efficiently collect current, and a current collector plate having a gold (Au) plating on the surface of a metal substrate is used.
  • a current collector plate having a gold (Au) plating on the surface of a metal substrate is used.
  • Au gold
  • JP 2003-217644 A (paragraph 0056) JP 2008-78104 A (paragraph 0090) JP 2008-146866 A (paragraph 0027) JP 2010-287542 A (paragraph 0149) WO2003 / 088395 pamphlet (page 3, line 10) JP 2009-152112 A (paragraph 0141)
  • an object of the present invention is to provide a current collector plate for a fuel cell that is excellent in cost performance, has low contact resistance, has excellent corrosion resistance, and can be used reliably over a long period of time.
  • Another object of the present invention is to provide a method for producing a current collector plate for a fuel cell, which can produce a current collector plate for a fuel cell having the above-described quality at a low cost.
  • the inventors of the present invention have made extensive studies in order to solve the problems of the prior art.
  • the nickel (Ni) plating film provided on the base of the Au plating film is caused by an increase in the contact resistance of the current collector plate.
  • the knowledge that it becomes important to control is obtained. Therefore, if the current collector plate uses an aluminum base material made of aluminum or an aluminum alloy and an Au plating film is formed on the surface of one side through a noble metal plating film, it prevents a decrease in performance due to the Ni plating film.
  • the inventors have found that the Au plating film can be used with excellent reliability over a long period of time while the film thickness of the Au plating film is made thinner than the conventional one, and the present invention has been completed.
  • the present invention is a current collector plate for a fuel cell that is disposed at both ends of a cell stack in which a plurality of fuel cell unit cells are stacked and used for taking out an electric current, and is an aluminum substrate made of aluminum or an aluminum alloy
  • a current collector plate for a fuel cell comprising:
  • the present invention also relates to a method of manufacturing a current collector plate for a fuel cell that is disposed at both ends of a cell stack in which a plurality of fuel cell unit cells are stacked and is used to extract current, and is made of aluminum or an aluminum alloy.
  • a method for producing a current collector plate for a fuel cell is disposed at both ends of a cell stack in which a plurality of fuel cell unit cells are stacked and is used to extract current, and is made of aluminum or an aluminum alloy.
  • an aluminum substrate made of aluminum or an aluminum alloy is used as a metal substrate, and a Ni plating film, a noble metal plating film, and an Au plating film are formed on one surface thereof.
  • E 0 25 ° C
  • Al is preferentially oxidized because Al is the most basic metal.
  • Ni when copper is used as the metal base material, Cu is a noble metal rather than Ni, so the base material cannot be a sacrificial anode, and the Ni oxidation inhibiting effect cannot be obtained.
  • the entire surface of the aluminum substrate is covered with each plating film, if the Ni plating film is exposed to an oxidizing atmosphere, Ni will be the most basic metal in each plating film, There is a possibility that Ni in the Ni plating layer is oxidized by the local battery reaction, thereby increasing the contact resistance.
  • the aluminum or aluminum alloy used for the aluminum substrate is not particularly limited.
  • high-purity aluminum JIS H4170; 1N99
  • various aluminum alloys a 5000 series aluminum alloy is preferable from the viewpoint of corrosion resistance, formability, strength, and cost.
  • Ni plating film mainly serves to prevent corrosion of the aluminum base material and to prevent Al of the aluminum base material from thermally diffusing to the surface of the Au plating film. Further, when an Au plating film to be formed later is performed by electroless plating treatment by a substitution reaction, it is used for the substitution reaction.
  • the film thickness of the Ni plating film is preferably 1 ⁇ m to 10 ⁇ m, more preferably 2 ⁇ m to 7 ⁇ m. If the film thickness is less than 1 ⁇ m, a portion that is not plated is generated, and the aluminum base material may be exposed when a noble metal plating film or an Au plating film described later is formed. On the other hand, if it is thicker than 10 ⁇ m, the cost increases, which is economically disadvantageous.
  • this Ni plating film can be formed by a known method, and may be electrolytic plating treatment, electroless plating treatment of reduction plating or displacement plating, but from the viewpoint of cost and uniformity of film thickness, Preferably, it is formed by electroless plating.
  • the conditions for the plating process vary depending on the type of plating process. For example, in the case of the electroless plating process, the bath temperature is about 70 to 100 ° C., and the immersion time is about 10 to 100 minutes. Good.
  • a noble metal plating film containing any one or more noble metals selected from the group consisting of Pd, Pt, Ag, Rh, Ir, Os, and Ru is formed.
  • This noble metal plating film plays a role of further enhancing the corrosion resistance of the current collector plate, and also prevents Ni from eluting from the crystal grain boundaries and pinholes of the Au plating film and depositing Ni oxide on the Au plating film. . Since the noble metal plating film plays these roles, it can have excellent corrosion resistance even if the thickness of the Au plating film formed on the noble metal plating film is made thinner than the conventional one, and the contact of the current collector plate An increase in resistance can be suppressed.
  • the noble metal plating film is preferably formed using Pd, Rh, Pt, Ru, or an alloy of these noble metals, and more preferably Pd, Rh, Ru, or these It may be formed using an alloy.
  • the film thickness of the noble metal plating film is preferably 0.01 ⁇ m to 0.1 ⁇ m, and preferably 0.02 ⁇ m to 0.08 ⁇ m. If the film thickness is less than 0.01 ⁇ m, a portion that is not plated is generated, the area where the Ni plating film is exposed becomes too large, and the corrosion resistance of the Ni plating film may be insufficient. On the other hand, if it is thicker than 0.1 ⁇ m, the cost increases and it is economically disadvantageous, and when the Au plating film described later is formed by a substitution reaction, the Ni plating film is completely covered and it is difficult to deposit Au. is there.
  • the replacement Au plating can proceed by exposing the Ni plating film from the crystal grain boundary of the noble metal plating film while suppressing the performance degradation of the current collector plate due to oxidation.
  • the noble metal plating film is preferably a crystalline noble metal plating film. That is, the noble metal plating film is made crystalline so as to have a grain boundary, and Ni used for forming the Au plating film is supplied through the noble metal film.
  • the bath temperature is preferably about 40 to 80 ° C.
  • the immersion time is preferably about 1 to 10 minutes.
  • a crystalline noble metal plating film when obtaining a crystalline noble metal plating film, either no eutectoid element is contained, or any one or more eutectoid elements selected from the group consisting of P, B, and W are added in an amount of 0 to You may make it contain in 3 mass%. That is, in order to obtain a crystalline noble metal plating film, the content of any one or more of the eutectoid elements is preferably in the range of 0 to 3% by mass. If the content of the eutectoid element is excessively increased, the noble metal plating film may become amorphous. However, if present in a small amount, the effect of making the noble metal plating film denser by reducing the grain boundary can be expected.
  • an Au plating film is formed thereon.
  • the Au plating film is most suitable from the viewpoint of lowering the contact resistance of the current collector plate, and it is desirable to increase the film thickness in order to increase the corrosion resistance, but the Au plating film is caused by the material. Will raise the price.
  • the film thickness of the Au plating film Is preferably 0.1 ⁇ m or less. However, if the thickness is too thin, defects such as pinholes may occur frequently.
  • the thickness of the Au plating film should be 0.01 ⁇ m or more, and is preferable from the viewpoint of uniformity of plating appearance, etc. Is preferably 0.01 ⁇ m to 0.08 ⁇ m, more preferably 0.02 ⁇ m to 0.06 ⁇ m.
  • Ni of the Ni plating film is preferably used. It is better to form by substitution reaction. That is, by obtaining a crystalline noble metal plating film in the step of forming the noble metal plating film, Ni eluted from the underlying Ni plating film through the grain boundary of the noble metal plating film can be used.
  • the treatment conditions for the electroless plating treatment by displacement plating are preferably a bath temperature of about 70 to 95 ° C. and an immersion time of about 10 to 70 minutes.
  • the crystal grain boundary of the noble metal plating film can be the starting point of the substitution reaction, so that the Au plating film can be uniformly formed on the surface of the noble metal plating film. Even if the thickness of the Au plating film is made thinner than that, sufficient performance can be exhibited in terms of corrosion resistance and contact resistance. Further, even if the Au plating film itself has a crystal grain boundary or some pinholes exist, the Au plating film blocks the grain boundary of the noble metal plating film, so that Ni elutes on the Au plating film. Can be suppressed. That is, Ni oxide (NiO) can be substantially absent from the surface of the Au plating film, and an increase in the contact resistance of the current collector plate can be prevented. The fact that Ni oxide is substantially absent means that NiO is formed from the intensity ratio of Ni and O by EDX (energy dispersive X-ray spectroscopy) analysis, as shown in the following examples. It means a state that can not be said.
  • EDX energy dispersive X-ray spectroscopy
  • the current collector plate in the present invention it is preferable to perform the zinc replacement treatment by immersing the aluminum base material in a zinc immersion bath prior to the formation of the Ni plating film.
  • a zinc immersion bath for example, an aqueous zinc oxide solution containing 4.1% by mass of zinc oxide, 25% by mass of sodium hydroxide, etc. can be diluted with ion-exchanged water to 400 ml / L and used. Is about 15 to 30 ° C., and the immersion time is about 10 seconds to 3 minutes.
  • the immersion zinc bath is removed by immersing in a pickling bath,
  • the substituted zinc layer may be formed by dipping in a zinc immersion bath again.
  • an acid aqueous solution having an acid of nitric acid, sulfuric acid, hydrochloric acid or the like and having a concentration of 10 to 65% by mass can be used. Seconds to about 1 minute.
  • the aluminum base material may be pretreated by a known method by performing a degreasing treatment, a desmut treatment, or the like before the zinc replacement treatment, or a connection terminal or the like may be formed on the aluminum base material by pressing. Then, after the Au plating film is formed, the current collector plate of the present invention can be obtained by washing with water and drying.
  • the outermost Au plating film has a thickness of 0.01 ⁇ m to 0.1 ⁇ m
  • the noble metal plating film has a thickness of 0.01 ⁇ m to 0.1 ⁇ m.
  • the anode current at a potential of 1 V measured by a corrosion current test for obtaining an anode polarization curve from a natural potential to 2 V at a potential sweep rate of 20 mV / min using a 5% sulfuric acid aqueous solution should be 1 mA / cm 2 or less. More preferably, it is 0.1 mA / cm 2 or less.
  • the contact resistance of the current collector plate immediately after production is 100
  • the contact resistance after 1500 hours in a constant temperature and high humidity environment at a temperature of 85 ° C. and a relative humidity of 95% is preferably 100 to 1000, More preferably, it is 100 to 500.
  • the present invention it is possible to obtain a current collector plate that has excellent corrosion resistance and suppresses an increase in contact resistance even if the Au plating film is made thinner than the conventional one. Therefore, the current collector plate for a fuel cell of the present invention can be used reliably over a long period of time while being excellent in cost.
  • FIG. 1 is a schematic side view illustrating a current collector plate for a fuel cell according to the present invention.
  • FIG. 2 is a schematic diagram ((a) side view, (b) perspective view) illustrating how the contact resistance of the test current collectors obtained in the examples and comparative examples is measured.
  • FIG. 3 is a graph showing the contact resistance of the test current collector obtained in the example.
  • FIG. 4 is a graph showing the contact resistance in the constant temperature and high humidity test of the test current collector plates obtained in Examples and Comparative Examples.
  • FIG. 5 is a graph showing the results of the corrosion current test of the test current collector plates obtained in the examples and comparative examples.
  • FIG. 6 is an optical micrograph (magnification 300 times) showing the state of the Au plating film before and after the nitric acid aeration test of the test current collector obtained in Example 1 [(a) Before the test, (b ) After the test].
  • FIG. 7 shows the EDX qualitative analysis results after leaving the test current collector obtained in Example 1 in a constant temperature and high humidity environment at 85 ° C. and a relative humidity of 95% for 750 hours.
  • FIG. 8 shows the SEM observation result (magnification 2000 times) of the Au plating film after leaving the test current collector obtained in Example 1 in a constant temperature and high humidity environment of 85 ° C. and relative humidity 95% for 750 hours. Show.
  • FIG. 9 is a TEM photograph (magnification: 45,000 times) showing a cross-sectional state of the Ni plating film and the Pd plating film of the test current collector plate obtained in Example 1.
  • FIG. 10 shows the result of XRD evaluation of the influence of the crystallinity of the Pd plating film depending on the eutectoid element content (when (a) containing 1% P, (b) containing 5% P).
  • FIG. 11 is an optical micrograph (magnification 300 times) showing the state of the Au plating film before and after the nitric acid aeration test of the test current collector obtained in Comparative Example 1 [(a) Before the test, (b ) After the test].
  • FIG. 10 shows the result of XRD evaluation of the influence of the crystallinity of the Pd plating film depending on the eutectoid element content (when (a) containing 1% P, (b) containing 5% P).
  • FIG. 11 is an optical micrograph (magnification 300 times
  • FIG. 12 shows the EDX qualitative analysis results after leaving the test current collector plate obtained in Comparative Example 1 in a constant temperature and high humidity environment at 85 ° C. and a relative humidity of 95% for 750 hours.
  • FIG. 13 shows the SEM observation results of the Au plating film after the test current collector obtained in Comparative Example 1 was left for 750 hours in a constant temperature and high humidity environment at 85 ° C. and 95% relative humidity.
  • FIG. 14 is an optical micrograph (magnification 300 times) showing the results of a nitric acid aeration test performed to confirm the sacrificial anodic action of the aluminum substrate [(a) Example product, (b) Comparative example product. ].
  • Example 1 [Preparation of current collector for testing] A 30 mm x 60 mm x 3 mm thick aluminum base material is cut out from a 3 mm thick aluminum alloy 5052-H34, and a weak alkaline degreasing agent (trade name: Top Alclean 161 manufactured by Okuno Pharmaceutical Co., Ltd.) is used at a concentration of 30 g / L. The sample was dipped in an aqueous solution diluted to 5 and degreased and washed at 55 ° C. for 5 minutes.
  • a weak alkaline degreasing agent trade name: Top Alclean 161 manufactured by Okuno Pharmaceutical Co., Ltd.
  • a desmutting solution containing nitric acid (trade name: Top Desmatt N-20, manufactured by Okuno Pharmaceutical Co., Ltd.) was immersed in an aqueous solution diluted to a concentration of 100 ml / L, and desmutting treatment was performed at 25 ° C. for 30 seconds.
  • a zinc treatment solution containing 25% by mass of sodium hydroxide and 4.1% by mass of zinc oxide (trade name: Substar, manufactured by Okuno Pharmaceutical Co., Ltd.)
  • the aluminum substrate was immersed for 30 seconds at 22 ° C. using a zinc immersion bath in which Zn-8) was diluted to a concentration of 400 ml / L.
  • an aqueous solution of nitric acid having a concentration of 62% by mass was used as a pickling bath, and the aluminum substrate was immersed for 30 seconds at 25 ° C., and the substituted zinc layer once formed on the surface of the aluminum substrate was peeled off.
  • the aluminum substrate was immersed at 22 ° C. for 30 seconds to form a substituted zinc layer of about 1 ⁇ m, and a zinc substitution treatment was performed.
  • a drug containing 19% by mass of sodium hypophosphite and 3.9% by mass of acetic acid (trade name: Top Nicolon RCH-MLF manufactured by Okuno Pharmaceutical Co., Ltd.) and 36% by mass of nickel acetate are contained.
  • the Ni plating solution (trade name: Top Nicolon RCH-1LF, manufactured by the same company) was diluted at 90 ° C. with a Ni plating bath that was diluted with water to a concentration of 130 ml / L and 40 ml / L, respectively. An electroless Ni plating treatment for immersion for 35 minutes was performed. As a result, a Ni plating film having a thickness of 5 ⁇ m was formed on one surface of the aluminum base opposite to the masked surface.
  • a chelating agent trade name manufactured by Okuno Pharmaceutical Co., Ltd .: Paratop LP-M
  • the drug containing 7% by mass of palladium salt trade name manufactured by the company
  • Paratop LP-A a drug containing 41% by mass of reducing agent
  • Paratop LP-C a
  • the film thickness of the Pd plating film is a value calculated from the immersion time because a 0.01 ⁇ m Pd plating film was deposited in an immersion time of 1 minute in an electroless Pd plating process separately performed in the same manner.
  • the contact resistance of the test current collector obtained above was measured as follows. As shown in FIG. 2 (a), the Au plating film side is brought into contact with the comparison plate 8, and these are sandwiched between the upper plate 7 and the lower plate 9, and a current collecting plate for testing while applying a surface pressure from above and below. A contact resistance value of 1 was measured. The results are shown in FIG.
  • the upper plate 7, the comparison plate 8, and the lower plate 9 each have a thickness of 0.1 ⁇ m through a Ni plating film having a thickness of 5 ⁇ m on both front and back surfaces of an aluminum plate (A5052 material) of 30 mm ⁇ 60 mm ⁇ 3 mm thickness. As shown in FIG.
  • a contact resistance measurement sample in which the vertical and horizontal directions are alternately stacked is prepared, and the test collector plate 1 and the comparison plate 8 are provided.
  • the contact resistance (m ⁇ ⁇ cm 2 ) was measured by measuring a voltage V between the test current collector 1 and the comparison plate 8 by passing a current I of 2 A between the upper plate 7 and the lower plate 9. It calculated
  • the contact resistance required for the current collector plate for a fuel cell is about 10 m ⁇ ⁇ cm 2 when the surface pressure is 1 MPa assuming a normal use mode. From the result shown in FIG. It has been found that the test current collector obtained in Example 1 exhibits extremely good contact resistance.
  • the current collector for testing obtained above is put in a constant temperature and high humidity tester, and a constant temperature and high humidity test is performed for 1500 hours in an environment of a temperature of 85 ° C. and a humidity of 95%. The contact resistance was measured at a surface pressure of 1 MPa. As a result, as shown in FIG.
  • the contact resistance of the test current collector obtained in Example 1 was 0.15 m ⁇ ⁇ cm 2 even after 1500 hours had elapsed, and the contact resistance immediately after fabrication was (0.05 m ⁇ ⁇ cm 2 ) was able to be suppressed to an increase of 300% (300 after 1500 hours when the contact resistance immediately after fabrication was taken as 100).
  • a corrosion current test was performed on the test current collector obtained in the same manner as described above as follows.
  • a test collector plate was placed in a 5% by mass sulfuric acid aqueous solution (400 ml, 30 ° C.) facing the platinum counter electrode, and a saturated calomel electrode was used as a reference electrode, and this reference electrode was immersed in a saturated potassium chloride aqueous solution. .
  • the saturated potassium chloride aqueous solution and the test collector plate are connected by a salt bridge, and the collector plate, the platinum counter electrode, and the saturated calomel electrode are connected to the potential stud, and 1 cm 2 of the Au plating film is used as the measurement area.
  • the potential of the current collector plate was scanned from the natural electrode potential to 2 V on the anode side at a potential sweep rate of 20 mV / min with respect to the saturated calomel electrode, and the electrochemical polarization characteristics evaluation method was used.
  • the corrosion current test was performed by measuring the peak current flowing through the current collector plate as the polarization current. As a result, as shown in FIG. 5, the anode current density measured at a potential of 1 V was 0.013 mA / cm 2 , confirming that the corrosion resistance was excellent.
  • FIG. 6A the photograph which observed the Au plating film after the test with the optical microscope is shown in FIG. 6B. (Both are 300 times magnification). As is apparent from these photographs, the Au plating film of the test current collector plate was not observed to have a poor appearance even after the nitric acid aeration test.
  • Ni oxide NiO
  • the detection depth of EDX was about 1 ⁇ m, and since the Ni plating film was as thick as 5 ⁇ m, the underlying Zn and the base material Al were not detected.
  • the constituent elements of the Pd plating film were analyzed using an electron beam microanalyzer (EPMA), it was confirmed that the Pd plating film contained 1% by mass of P as a eutectoid element.
  • EPMA 1610 manufactured by Shimadzu Corporation was used for EPMA analysis, and the analysis was performed under the condition of an acceleration voltage of 15 kV.
  • the crystallinity of the Pd plating film was confirmed by XRD as follows.
  • an electroless Pd plating treatment in which a separately prepared Ni plate is immersed at 60 ° C. for 5 minutes is performed, and the film thickness contains 1% by mass of P as a eutectoid element.
  • a 0.05 ⁇ m Pd plating film was formed on the Ni plate.
  • Example 1 Comparative Example 1 After the Ni plating film was formed, the Pd plating film (noble metal plating film) was not formed, but the Au plating film was formed with a film thickness of 0.08 ⁇ m. A current collector plate was obtained. The obtained test collector plate was evaluated in the same manner as in Example 1 as follows.
  • the contact resistance immediately after fabrication was lower than that obtained in Example 1 for any contact pressure, but as shown in FIG.
  • the contact resistance starts increasing after about 500 hours in the high humidity test, reaches 0.45 m ⁇ ⁇ cm 2 after 1500 hours, and increases by 1000% with respect to the contact resistance (0.04 m ⁇ ⁇ cm 2 ) immediately after fabrication. did.
  • the corrosion current test the anode current density measured at a potential of 1 V was 2.8 mA / cm 2 , indicating that the corrosion resistance was poor.
  • test current collector plate of Comparative Example 1 obtained in the same manner as described above was allowed to stand in a constant temperature and high humidity environment at 85 ° C. and a relative humidity of 95% for 750 hours, followed by a scanning electron microscope (SEM) equipped with EDX. ) was used to analyze the chemical composition of the compounds contained in the plating film on the aluminum substrate.
  • SEM scanning electron microscope
  • FIG. 12 The qualitative analysis result by EDX is shown in FIG. 12, and the SEM observation result is shown in FIG. According to SEM observation, it can be seen that there are a large number of bulges and pleated precipitates on the surface of the Au plating film.
  • Example 2 Using a Pd plating bath, an electroless Pd plating treatment of immersing at 60 ° C. for 10 minutes was performed, and a Pd plating film having a film thickness of 0.1 ⁇ m was formed on the Ni plating film. A test current collector plate according to Example 2 was obtained. The obtained test collector plate was evaluated in the same manner as in Example 1 as follows.
  • the contact resistance immediately after fabrication is generally lower than the contact resistance required for a current collector for a fuel cell for any surface pressure, and as shown in FIG. Even after 1500 hours have elapsed, the contact resistance of the test current collector obtained in Example 2 is 0.09 m ⁇ ⁇ cm 2 , compared to the contact resistance immediately after fabrication (0.05 m ⁇ ⁇ cm 2 ). The increase was 180%. Further, as shown in FIG. 5, in the corrosion current test, the anode current density measured at a potential of 1 V was 0.0028 mA / cm 2 , indicating that the corrosion resistance was excellent.
  • Example 2 In the course of obtaining the test current collector plate of Example 2, when a Pd plating film having a film thickness of 0.1 ⁇ m was formed by electroless Pd plating, the cross section was observed by TEM in the same manner as in Example 1. The Pd plating film was confirmed to be crystalline with crystal grain boundaries.
  • Example 3 Comparative Examples 2 to 3
  • each plating film was formed as shown in Table 1, and current collector plates for tests of Example 3 and Comparative Examples 2 to 3 were obtained. It was. That is, in Example 3, except that the above-mentioned aluminum base material was used, the same procedure as in Example 1 was carried out. As a result, a test current collector plate evaluated almost the same as in Example 1 was obtained.
  • Comparative Examples 2 to 3 in the same manner as Comparative Example 1 except that the film thickness of the Au plating film was changed in addition to the change of the aluminum base material, contact after 1500 hours had passed in the constant temperature and high humidity test In all cases, the resistance increased by 1000% or more with respect to the contact resistance immediately after production, and as a result of the corrosion current test, it was found that the resistance was inferior. Furthermore, with respect to the Au plating film after being left for 750 hours in a constant temperature and high humidity environment of 85 ° C. and a relative humidity of 95%, many blisters and pleated precipitates were confirmed by SEM observation. Furthermore, in the Au plating film after the nitric acid aeration test, traces such as cracks and peeling were confirmed, and the appearance was inferior.
  • Example 2 the comparative sample in which the aluminum base material was not exposed at all and the test current collector (no mask) obtained in the same manner as in Example 1 were simultaneously placed in a desiccator in the same manner as in Example 1. A nitrate aeration test was conducted.
  • FIG. 14A is an optical micrograph of the Au plating film of the test current collector obtained in the same manner as in Example 1, and no change in appearance was observed.
  • FIG. 14B shows the case of a comparative sample in which an aluminum substrate is masked, and blisters such that a part of the Au plating film swells were observed, and fine cracks were confirmed in part.
  • the current collector plate of the present invention that forms a plating film on one surface of an aluminum substrate, the oxidation of Ni is suppressed by the sacrificial anodic action of the aluminum substrate. I understand that I can do it.
  • 1 current collector plate for fuel cell
  • 2 aluminum base material
  • 3 substituted zinc layer
  • 4 Ni plating film
  • 5 noble metal plating film
  • 6 Au plating film
  • 7 upper plate
  • 8 comparison plate
  • 9 Lower plate.

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PCT/JP2012/076939 2011-11-14 2012-10-18 燃料電池用集電板及びその製造方法 Ceased WO2013073330A1 (ja)

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EP12850407.3A EP2782177A4 (en) 2011-11-14 2012-10-18 FUEL BOARD FOR FUEL CELLS AND METHOD FOR THE PRODUCTION THEREOF
US14/357,788 US20140308602A1 (en) 2011-11-14 2012-10-18 Collector plate for fuel cells and method for producing same
CN201280055735.3A CN103931034B (zh) 2011-11-14 2012-10-18 燃料电池用集电板及其制造方法

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WO2014208610A1 (ja) * 2013-06-28 2014-12-31 日本軽金属株式会社 導電部材
US9633957B2 (en) * 2014-11-28 2017-04-25 Infineon Technologies Ag Semiconductor device, a power semiconductor device, and a method for processing a semiconductor device
JP6587848B2 (ja) * 2015-07-09 2019-10-09 東洋鋼鈑株式会社 燃料電池用通電部材、燃料電池セル、燃料電池スタック、及び燃料電池用通電部材の製造方法
JP2017152225A (ja) * 2016-02-25 2017-08-31 パナソニックＩｐマネジメント株式会社 燃料電池用集電板
CN107146899A (zh) * 2016-03-01 2017-09-08 中国科学院大连化学物理研究所 质子交换膜燃料电池不锈钢双极板表面涂层结构及制备
CN112687905A (zh) * 2020-12-26 2021-04-20 上海捷氢科技有限公司 一种燃料电池阳极集流板及燃料电池电堆
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CN103931034B (zh) 2016-10-26
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US20140308602A1 (en) 2014-10-16
CN103931034A (zh) 2014-07-16
TW201347285A (zh) 2013-11-16
EP2782177A1 (en) 2014-09-24
JP2013105629A (ja) 2013-05-30
JP5590008B2 (ja) 2014-09-17

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