METAL SHEET FOR SEPARATORS OF POLYMER ELECTROLYTE FUEL CELLS

Abstract

A metal sheet for separators of polymer electrolyte fuel cells having both excellent corrosion resistance in the use environment of separators of polymer electrolyte fuel cells and excellent adhesion property between a substrate and a surface-coating layer even in the case where the surface-coating layer is made thinner is provided. A metal sheet for separators of polymer electrolyte fuel cells includes: a substrate made of metal; and a surface-coating layer with which the substrate is coated, with a strike layer in between, wherein a coating weight of the strike layer is 0.001 g/m.sup.2 to 1.0 g/m.sup.2.

Claims

1. A metal sheet for separators of polymer electrolyte fuel cells, comprising: a substrate made of metal; and a surface-coating layer with which a surface of the substrate is coated, with a strike layer in between, wherein a coating weight of the strike layer is 0.001 g/m.sup.2 to 1.0 g/m.sup.2.

2. The metal sheet for separators of polymer electrolyte fuel cells according to claim 1, wherein the strike layer contains at least one element selected from the group consisting of Ni, Cu, Ag, and Au.

3. The metal sheet for separators of polymer electrolyte fuel cells according to claim 1, wherein the strike layer is made of an alloy layer of Ni and P, and has a P content in a range of 5 mass % to 22 mass %.

4. The metal sheet for separators of polymer electrolyte fuel cells according to claim 1, wherein the surface-coating layer is made of a metal layer, an alloy layer, a metal oxide layer, a metal nitride layer, a metal carbide layer, a carbon material layer, a conductive polymer layer, an organic resin layer containing a conductive substance, or a mixed layer thereof.

5. The metal sheet for separators of polymer electrolyte fuel cells according to claim 1, wherein the surface-coating layer is made of a Sn alloy layer, and the metal sheet for separators of polymer electrolyte fuel cells further comprises a Sn-containing oxide layer on a surface of the surface-coating layer.

6. The metal sheet for separators of polymer electrolyte fuel cells according to claim 2, wherein the surface-coating layer is made of a metal layer, an alloy layer, a metal oxide layer, a metal nitride layer, a metal carbide layer, a carbon material layer, a conductive polymer layer, an organic resin layer containing a conductive substance, or a mixed layer thereof.

7. The metal sheet for separators of polymer electrolyte fuel cells according to claim 3, wherein the surface-coating layer is made of a metal layer, an alloy layer, a metal oxide layer, a metal nitride layer, a metal carbide layer, a carbon material layer, a conductive polymer layer, an organic resin layer containing a conductive substance, or a mixed layer thereof.

8. The metal sheet for separators of polymer electrolyte fuel cells according to claim 2, wherein the surface-coating layer is made of a Sn alloy layer, and the metal sheet for separators of polymer electrolyte fuel cells further comprises a Sn-containing oxide layer on a surface of the surface-coating layer.

9. The metal sheet for separators of polymer electrolyte fuel cells according to claim 3, wherein the surface-coating layer is made of a Sn alloy layer, and the metal sheet for separators of polymer electrolyte fuel cells further comprises a Sn-containing oxide layer on a surface of the surface-coating layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0056] In the accompanying drawings:

[0057] FIG. 1 is a schematic diagram illustrating the basic structure of a fuel cell.

DETAILED DESCRIPTION

[0058] Detailed description is given below.

[0059] (1) Metal Sheet Used as Substrate

[0060] A metal sheet used as a substrate in the disclosure is not particularly limited, but a stainless steel sheet (ferritic stainless steel sheet, austenitic stainless steel sheet, dual-phase stainless steel sheet), a titanium sheet, a titanium alloy sheet, and the like having excellent corrosion resistance are particularly advantageous.

[0061] For example, as the stainless steel sheet, SUS447J1 (Cr: 30 mass %, Mo: 2 mass %), SUS445J1 (Cr: 22 mass %, Mo: 1 mass %), SUS443J1 (Cr: 21 mass %), SUS439 (Cr: 18 mass %), SUS316L (Cr: 18 mass %, Ni: 12 mass %, Mo: 2 mass %), or the like is suitable. SUS447J1 containing about 30 mass % Cr has high corrosion resistance, and so is particularly advantageous as the substrate for separators of polymer electrolyte fuel cells used in an environment where high corrosion resistance is required. As the titanium sheet, JIS 1 type or the like is suitable. As the titanium alloy sheet, JIS 61 type or the like is suitable.

[0062] In view of the installation space or weight when stacking fuel cells, the sheet thickness of the metal sheet for separators is preferably in the range of 0.03 mm to 0.3 mm. If the sheet thickness of the metal sheet for separators is less than 0.03 mm, the production efficiency of the metal sheet decreases. If the sheet thickness of the metal sheet for separators is more than 0.3 mm, the installation space or weight when stacking fuel cells increases. The sheet thickness of the metal sheet for separators is more preferably 0.03 mm or more and 0.1 mm or less.

[0063] (2) Surface-Coating Layer

[0064] A surface-coating layer with which the surface of the substrate is coated is not limited, but a material excellent in corrosion resistance and conductivity in the use environment (pH: 3 (sulfuric acid environment), use temperature: 80 C.) of separators of polymer electrolyte fuel cells is preferably used. For example, a metal layer, an alloy layer, a metal oxide layer, a metal carbide layer, a metal nitride layer, a carbon material layer, a conductive polymer layer, an organic resin layer containing a conductive substance, or a mixed layer thereof is suitable.

[0065] Examples of the metal layer include metal layers of Au, Ag, Cu, Pt, Pd, W, Sn, Ti, Al, Zr, Nb, Ta, Ru, Ir, and Ni. A metal layer of Au or Pt is particularly suitable.

[0066] Examples of the alloy layer include Sn alloy layers of NiSn (Ni.sub.3Sn.sub.2, Ni.sub.3Sn.sub.4), CuSn (Cu.sub.3Sn, Cu.sub.6Sn.sub.5), FeSn (FeSn, FeSn.sub.2), SnAg, and SnCo, and alloy layers of NiW, NiCr, and TiTa. An alloy layer of NiSn or FeSn is particularly suitable.

[0067] Examples of the metal oxide layer include metal oxide layers of SnO.sub.2, ZrO.sub.2, TiO.sub.2, WO.sub.3, SiO.sub.2, Al.sub.2O.sub.3, Nb.sub.2O.sub.5, IrO.sub.2, RuO.sub.2, PdO.sub.2, Ta.sub.2O.sub.5, Mo.sub.2O.sub.5, and Cr.sub.2O.sub.3. A metal oxide layer of TiO.sub.2 or SnO.sub.2 is particularly suitable.

[0068] Examples of the metal nitride layer and the metal carbide layer include metal nitride layers and metal carbide layers of TiN, CrN, TiCN, TiAlN, AlCrN, TiC, WC, SiC, B.sub.4C, molybdenum nitride, CrC, TaC, and ZrN. A metal nitride layer of TiN is particularly suitable.

[0069] Examples of the carbon material layer include carbon material layers of graphite, diamond, amorphous carbon, diamond-like carbon, carbon black, fullerene, and carbon nanotube. A carbon material layer of graphite or diamond-like carbon is particularly suitable.

[0070] Examples of the conductive polymer layer include conductive polymer layers of polyaniline and polypyrrole.

[0071] The organic resin layer containing a conductive substance contains at least one conductive substance selected from a metal, an alloy, a metal oxide, a metal nitride, a metal carbide, a carbon material, and a conductive polymer included in the aforementioned metal layer, alloy layer, metal oxide layer, metal nitride layer, metal carbide layer, carbon material layer, and conductive polymer layer, and contains at least one organic resin selected from epoxy resin, phenol resin, polyamide-imide resin, polyester resin, polyphenylene sulfide resin, polyamide resin, urethane resin, acrylic resin, polyethylene resin, polypropylene resin, carbodiimide resin, phenol epoxy resin, and the like. As the organic resin layer containing a conductive substance, for example, graphite-dispersed phenol resin or carbon black-dispersed epoxy resin is suitable.

[0072] As the conductive substance, a metal and a carbon material (in particular, graphite, carbon black) are suitable. The content of the conductive substance is not limited, as long as predetermined conductivity is obtained in separators of polymer electrolyte fuel cells.

[0073] Examples of the mixed layer include a mixed layer of a TiN-dispersed NiSn alloy.

[0074] For the formation of the surface-coating layer on the surface of the metal substrate, a method such as plating, physical vapor deposition (PVD), chemical vapor deposition (CVD), electrodeposition, thermal spraying, surface melting treatment, or coating may be used depending on the type of the surface-coating layer to be formed.

[0075] For example, in the case of providing the surface-coating layer that is the metal layer or the alloy layer, plating is suitable. In this case, by a conventionally known plating method the substrate is immersed in a plating bath adjusted to a predetermined composition and subjected to electroplating, electroless plating, or hot dip coating. The thickness of such a surface-coating layer is preferably 0.1 m or more and 5 m or less. If the thickness of the surface-coating layer is less than 0.1 m, coating defects increase and the corrosion resistance tends to degrade. If the thickness of the surface-coating layer is more than 5 m, the coating cost increases and manufacturability decreases. The thickness of the surface-coating layer is more preferably 0.5 m or more. The thickness of the surface-coating layer is more preferably 3 m or less.

[0076] In the case of providing the metal oxide layer, the metal nitride layer, the metal carbide layer, or the carbon material layer, physical vapor deposition (PVD) or chemical vapor deposition (CVD) is suitable. The thickness of such a surface-coating layer is preferably in the range of 0.05 m to 1 m, for the same reason as above.

[0077] In the case of providing the conductive polymer layer, electropolymerization is suitable. The thickness of such a surface-coating layer is preferably in the range of 0.1 m to 5 m, for the same reason as above.

[0078] In the case of providing the organic resin layer containing a conductive substance, coating (a method of applying a predetermined coating solution and then firing) is suitable. The thickness of such a surface-coating layer is preferably in the range of 1 m to 50 m, for the same reason as above. The thickness of the surface-coating layer is more preferably 1 m or more. The thickness of the surface-coating layer is more preferably 10 m or less.

[0079] (Strike Layer)

[0080] In the disclosure, a strike layer is formed between the metal substrate and the surface-coating layer to improve the adhesion between the layer and the substrate. The reason why forming the strike layer between the metal substrate and the surface-coating layer improves the adhesion between the surface-coating layer and the substrate appears to be as follows.

[0081] In the case where there is no strike layer, an inactive passive film or the like tends to be formed on the surface of the metal substrate, making it difficult to achieve high adhesion. In the case where the strike layer is provided, on the other hand, the formation of the passive film or the like is suppressed and the surface of the metal substrate is kept from becoming inactive, as a result of which the adhesion between the substrate and the surface-coating layer is improved.

[0082] Moreover, a strike layer whose surface is uneven is more advantageous because the adhesion is further improved by the anchor effect.

[0083] The disclosed metal sheet for separators of polymer electrolyte fuel cells thus has excellent adhesion between the substrate and the surface-coating layer, and therefore is advantageous in the process of forming the separator into a desired shape or the process of assembling the fuel cell where high adhesion is required, or when the fuel cell vibrates violently during use.

[0084] In the disclosure, it is very important to limit the coating weight of the strike layer to the following range:

[0085] the coating weight of the strike layer: 0.001 g/m.sup.2 to 1.0 g/m.sup.2.

[0086] By limiting the coating weight of the strike layer to this range, the corrosion resistance in the separator use environment can be maintained even in the case where the surface-coating layer is made thinner. The reason for this appears to be as follows.

[0087] Typically, when the thickness of the surface-coating layer is reduced, in-layer defects from the surface-coating layer to the substrate increase. Through these defects, the strike layer between the metal substrate and the surface-coating layer is widely corroded continuously in the surface direction, causing the surface-coating layer above the strike layer to exfoliate from the metal substrate. When the surface-coating layer exfoliates, the substrate is exposed to the separator use environment, and as a result the corrosion resistance decreases.

[0088] Limiting the coating weight of the strike layer to a very low range, however, allows the strike layer to be formed discontinuously on the surface of the substrate. In other words, a discontinuous portion such as a non-plating area of the strike layer appears in part of the surface of the substrate. This discontinuous portion of the strike layer acts as an area that inhibits the propagation of the corrosion. Hence, the continuous corrosion of the strike layer is suppressed even in the case where the surface-coating layer is made thinner. The degradation of the corrosion resistance can be prevented in this way.

[0089] If the coating weight of the strike layer is less than 0.001 g/m.sup.2, the adhesion between the metal substrate and the surface-coating layer decreases. If the coating weight of the strike layer is more than 1.0 g/m.sup.2, the corrosion resistance cannot be maintained in the case where the thickness of the surface-coating layer is reduced. Accordingly, the coating weight of the strike layer is limited to the range of 0.001 g/m.sup.2 to 1.0 g/m.sup.2. The coating weight of the strike layer is preferably 0.003 g/m.sup.2 or more. The coating weight of the strike layer is preferably 0.5 g/m.sup.2 or less. The coating weight of the strike layer is more preferably 0.003 g/m.sup.2 or more. The coating weight of the strike layer is more preferably 0.3 g/m.sup.2 or less. The coating weight of the strike layer is further preferably 0.005 g/m.sup.2 or more. The coating weight of the strike layer is further preferably 0.05 g/m.sup.2 or less.

[0090] The strike layer is preferably a metal layer of Ni, Cu, Ag, Au, or the like or an alloy layer containing at least one selected from these elements. A Ni strike or a NiP strike made of an alloy layer of Ni and P is more preferable in terms of material cost.

[0091] In the case of a NiP strike, it is further preferable to limit the P content in the NiP strike layer to the range of 5 mass % to 22 mass %.

[0092] P content in NiP strike layer: 5 mass % to 22 mass %

[0093] By limiting the P content in the NiP strike layer to this range, excellent corrosion resistance can be maintained more stably even in the event of long exposure to high potential in the separator environment. The reason for this appears to be as follows.

[0094] By limiting the P content in the NiP strike layer to the range of 5 mass % to 22 mass %, a more stable NiP compound in the separator use environment is formed, with it being possible to suppress the corrosion of the strike layer effectively for a longer time.

[0095] If the P content in the NiP strike layer is less than 5 mass %, the acid resistance improvement effect of the NiP compound is insufficient. Such a range is not preferable in terms of maintaining excellent corrosion resistance in the event of long exposure to high potential in the separator environment which is acid. If the P content in the NiP strike layer is more than 22 mass %, the composition of the NiP strike tends to be not uniform. Such a range is also not preferable in terms of maintaining excellent corrosion resistance in the event of long exposure to high potential in the separator environment. Therefore, the P content in the NiP strike layer is preferably limited to the range of 5 mass % to 22 mass %. The P content in the NiP strike layer is more preferably 7 mass % or more. The P content in the NiP strike layer is more preferably 20 mass % or less. The P content in the NiP strike layer is further preferably 10 mass % or more. The P content in the NiP strike layer is further preferably 18 mass % or less.

[0096] The method of forming the strike layer may be a conventionally known plating method whereby electroplating or electroless plating is performed in a plating bath adjusted to an appropriate composition. The coating weight of the strike layer is adjustable by the time of retention in the plating bath, i.e. the plating time.

[0097] The P content in the NiP strike layer is adjustable by the P concentration in the plating bath, the current density in electroplating, or the like.

[0098] (4) Sn-Containing Oxide Layer

[0099] In the disclosed metal sheet for separators, in the case where the surface-coating layer is a layer made of a Sn alloy (Sn alloy layer), the surface of the Sn alloy layer is preferably coated with a Sn-containing oxide layer. This further improves the corrosion resistance after long use in the separator use environment.

[0100] The Sn-containing oxide layer with which the surface of the Sn alloy layer is coated is not a natural oxide layer created in the atmospheric environment but an oxide layer deliberately formed by a process such as immersion in an acid solution. The thickness of the natural oxide layer is typically about 2 nm to 3 nm.

[0101] The main component of the Sn-containing oxide layer is preferably SnO.sub.2. The thickness of the Sn-containing oxide layer is preferably 5 nm or more. The thickness of the Sn-containing oxide layer is preferably 100 nm or less. The thickness of the Sn-containing oxide layer is more preferably 10 nm or more. The thickness of the Sn-containing oxide layer is more preferably 30 nm or less. If the Sn-containing oxide layer is excessively thick, the conductivity decreases. If the Sn-containing oxide layer is excessively thin, the corrosion resistance improvement effect in the separator use environment cannot be achieved.

[0102] The reason why coating the surface of the Sn alloy layer with the Sn-containing oxide layer improves the corrosion resistance after long use in the separator use environment appears to be as follows. Since the Sn-containing oxide layer is very stable in the separator use environment, coating the surface of the surface-coating layer with the Sn-containing oxide layer suppresses the corrosion of the surface-coating layer effectively.

[0103] Here, the oxide layer is deliberately formed by a process such as immersion in an acid solution instead of using a natural oxide layer, for the following reason. Through such a process, the oxide layer can be uniformly and accurately formed on the surface of the surface-coating layer, with it being possible to suppress the corrosion of the surface-coating layer very effectively.

[0104] The Sn-containing oxide layer may be formed by a method of immersion in an acid aqueous solution having oxidizability such as hydrogen peroxide or nitric acid, or a method of anodic electrolysis.

[0105] For example, the Sn-containing oxide layer can be formed by applying anodic electrolysis, in a sulfuric acid aqueous solution of a temperature of 60 C. and a pH of 1 for 5 minutes with a current density of +1 mA/cm.sup.2, to the metal sheet for separators having the surface-coating layer.

[0106] The method of forming the Sn-containing oxide layer is not limited to the above. Other examples include physical vapor deposition (PVD), chemical vapor deposition (CVD), and coating.

[0107] (5) Other Features

[0108] After forming the surface-coating layer on the surface of the metal substrate with the strike layer in between or after forming the Sn alloy layer on the surface of the metal substrate with the strike layer in between and then forming the Sn-containing oxide layer, a conductive layer with lower electric resistance may be further formed on the surface-coating layer or the Sn-containing oxide layer, to improve the conductivity which is one of the required properties of separators. For example, the surface-coating layer or the Sn-containing oxide layer may be coated with a metal layer, a conductive polymer layer, an alloy layer including conductive particles, or a polymer layer including conductive particles, in order to reduce the contact resistance.

EXAMPLES

[0109] Separators of polymer electrolyte fuel cells are used in a severe corrosion environment of about 80 C. in temperature and 3 in pH, and therefore excellent corrosion resistance is required. Moreover, high adhesion between the metal substrate and the surface-coating layer is required so that the surface-coating layer does not peel off the metal substrate in the fuel cell manufacturing process such as the process of forming the separator into a desired shape or the process of assembling the fuel cell. In view of these required properties, the following two types of evaluation were conducted on the below-mentioned samples.

[0110] (1) Evaluation of Corrosion Resistance (Stability in Separator Use Environment)

[0111] Each sample was immersed in a sulfuric acid aqueous solution of a temperature of 80 C. and a pH of 3 and applied at a constant potential of 0.9 V (vs. SHE) for 20 hours using Ag/AgCl (saturated KCl aqueous solution) as a reference electrode, and the current density after 20 hours was measured. Based on the current density after 20 hours, the corrosion resistance after 20 hours in the separator use environment was evaluated by the following criteria. [0112] Pass (excellent): the current density after 20 hours was less than 0.015 A/cm.sup.2. [0113] Pass: the current density after 20 hours was 0.015 A/cm.sup.2 or more and less than 0.2 A/cm.sup.2. [0114] Fail: the current density after 20 hours was 0.2 A/cm.sup.2 or more.

[0115] (2) Evaluation of Adhesion Property

[0116] The adhesive face of Scotch tape was adhered to the surface of each sample obtained by forming a surface-coating layer on the surface of a metal substrate, in an area of 20 mm20 mm. The Scotch tape was then removed, and the adhesion property was evaluated by the following criteria. [0117] Pass: the surface-coating layer did not peel after the removal of the Scotch tape. [0118] Fail: the surface-coating layer peeled after the removal of the Scotch tape.

Example 1

[0119] Each of SUS447J1 (Cr: 30 mass %) of 0.05 mm in sheet thickness and titanium JIS 1 type of 0.05 mm in sheet thickness as a substrate was subjected to appropriate pretreatment such as degreasing, and then a strike layer with a coating weight in Table 1 was formed on the substrate using the following plating bath composition and plating condition. Next, a surface-coating layer with an average thickness in Table 1 was formed on the substrate having the strike layer, to obtain a metal sheet for separators.

[0120] For the metal layer and alloy layer of Au and Ni.sub.3Sn.sub.2 and TiN-dispersed Ni.sub.3Sn.sub.2, the surface-coating layer was formed using the following plating bath composition and plating condition. For the metal oxide layers of TiO.sub.2 and SnO.sub.2, the surface-coating layer was formed by physical vapor deposition (PVD). For the metal nitride layer (TiN), the surface-coating layer was formed by physical vapor deposition (PVD). For the carbon material layer (diamond-like carbon), the surface-coating layer was formed by chemical vapor deposition (CVD). For the conductive polymer layer (polyaniline), the surface-coating layer was formed by electropolymerization. For the organic resin layer containing a conductive substance (carbon black-dispersed epoxy resin and graphite-dispersed phenol resin), the surface-coating layer was formed by applying a predetermined coating solution and then firing.

[0121] In sample No. 29, the obtained metal sheet for separators was subjected to anodic electrolysis in a sulfuric acid aqueous solution of a temperature of 60 C. and a pH of 1 for 5 minutes with a current density of +1 mA/cm.sup.2, to form a Sn-containing oxide layer on the surface of the surface-coating layer.

[0122] Each property was evaluated in the aforementioned manner using the obtained metal sheet for separators.

[0123] The coating weight of the strike layer, the average thickness of the surface-coating layer, and the average thickness of the Sn-containing oxide layer were each regulated by determining the relationship with the plating time, the anodic electrolysis time, the layer formation time in physical vapor deposition (PVD) or chemical vapor deposition (CVD), and the amount of the coating solution applied in the coating beforehand. For comparison, a metal sheet for separators having no strike layer was also prepared, and each property was evaluated in the aforementioned manner.

[0124] The coating weight of the strike layer was measured by the following method. First, each sample obtained by forming the strike layer on the surface of the substrate (0.05 mm in thickness) was cut to about 50 mm W50 mm L, the lengths of two sides were measured by a caliper square, and the sample area was calculated. The sample was then immersed in a solution in which the strike layer can be dissolved (a known dissociation solution may be used, such as 30% nitric acid for Ni, NiP, or Cu strike, 90% sulfuric acid+10% nitric acid for Ag strike, and 30 g/L sodium cyanide+40 mL/L hydrogen peroxide for Au strike) for 10 minutes to dissolve the strike layer. The constituent element of the strike layer dissolved in the solution was quantified using an inductively coupled plasma (ICP) emission spectrometric analyzer, and the sample area was divided by the quantification result, thus yielding the coating weight (g/m.sup.2). Regarding the samples having no strike, is set in the field of the coating weight of the strike layer in Table 1.

[0125] The average thickness of the surface-coating layer was measured by the following method. The measurement method in the case where the average thickness is 1 m or more is described first. Each sample obtained by forming the strike layer and the surface-coating layer on the surface of the substrate (0.05 mm in thickness) was cut to about 10 mm W15 mm L. The sample was then embedded in resin, polished in the cross section, and then observed using a scanning electron microscope (SEM) to measure the thickness of the surface-coating layer. The measurement of the thickness of the surface-coating layer was performed on 10 samples obtained by cutting the same sample having the surface-coating layer to the aforementioned shape, and the average thickness of these samples was set as the average thickness of the surface-coating layer.

[0126] The measurement method in the case where the average thickness of the surface-coating layer is less than 1 m and the method of measuring the average thickness of the Sn-containing oxide layer are described next. Each sample obtained by forming the strike layer and the surface-coating layer and, for No. 29, further the Sn-containing oxide layer on the surface of the substrate (0.05 mm in thickness) was processed by a focused ion beam to prepare a thin film for cross-section observation. The produced thin film for cross-section observation was then observed using a transmission electron microscope (TEM), to measure the average thickness of each of the surface-coating layer and the Sn-containing oxide layer. In the measurement of the average thickness of each of the surface-coating layer and the Sn-containing oxide layer, the thickness of each of the surface-coating layer and the Sn-containing oxide layer in the prepared thin film for cross-section observation was measured at three locations, and the average value of the three locations was set as the average thickness of the corresponding one of the surface-coating layer and the Sn-containing oxide layer.

[0127] Here, the composition of each of the surface-coating layer and the Sn-containing oxide layer was identified by an energy-dispersive X-ray spectrometer (EDX), X-ray diffractometer (XRD), laser Raman spectrometer, and/or Fourier transform infrared spectroscopic analyzer used in the SEM observation or TEM observation.

[0128] (Plating Bath Composition and Plating Condition of Strike Layer)

<Ni Strike>

[0129] Nickel chloride: 240 g/L

[0130] Hydrochloric acid: 125 ml/L

[0131] Temperature: 50 C.

[0132] Current density: 5 A/dm.sup.2

<NiP Strike>

[0133] Nickel sulfate: 1 mol/L

[0134] Nickel chloride: 0.1 mol/L

[0135] Boric acid: 0.5 mol/L

[0136] Sodium phosphite: 0.05 mol/L to 5 mol/L

[0137] Temperature: 50 C.

[0138] Current density: 5 A/dm.sup.2

<Cu Strike>

[0139] Copper cyanide: 30 g/L

[0140] Sodium cyanide: 40 g/L

[0141] Potassium hydroxide: 4 g/L

[0142] Temperature: 40 C.

[0143] Current density: 5 A/dm.sup.2

<Ag Strike>

[0144] Silver potassium cyanide: 2 g/L

[0145] Sodium cyanide: 120 g/L

[0146] Temperature: 30 C.

[0147] Current density: 3 A/dm.sup.2

<Au>

[0148] Gold potassium cyanide: 8 g/L

[0149] Sodium citrate: 80 g/L

[0150] Nickel sulfamate: 3 g/L

[0151] Zinc acetate: 0.3 g/L

[0152] Temperature: 30 C.

[0153] Current density: 3 A/dm.sup.2

[0154] (Plating Bath Composition and Plating Condition of Surface-Coating Layer)

<Au>

[0155] Gold potassium cyanide: 8 g/L

[0156] Sodium citrate: 80 g/L

[0157] Nickel sulfamate: 3 g/L

[0158] Zinc acetate: 0.3 g/L

[0159] Temperature: 30 C.

[0160] Current density: 1 A/dm.sup.2

<Ni.sub.3Sn.sub.2>

[0161] Nickel chloride: 0.15 mol/L

[0162] Tin chloride: 0.15 mol/L

[0163] Potassium pyrophosphate: 0.45 mol/L

[0164] Glycine: 0.15 mol/L

[0165] Temperature: 60 C.

[0166] Current density: 1 A/dm.sup.2

<TiN-Dispersed Ni.sub.3Sn.sub.2>

[0167] Nickel chloride: 0.15 mol/L

[0168] Tin chloride: 0.15 mol/L

[0169] Potassium pyrophosphate: 0.45 mol/L

[0170] Glycine: 0.15 mol/L

[0171] Temperature: 60 C.

[0172] Current density: 1 A/dm.sup.2

[0173] Average particle size of dispersed TiN: 1.5 m

[0174] In the disclosure, as long as a desired plating can be formed, a plating bath composition other than the above may be used according to a known plating method.

[0175] Table 1 summarizes the results of evaluating the corrosion resistance (stability in the separator use environment) and the adhesion property for each sample obtained as described above.

TABLE-US-00001 TABLE 1 Sample preparation condition Strike layer Surface-coating layer Sn-containing oxide layer Current Peeling of Evaluation result Coating Average Average density after surface-coating Corrosion Sample weight P content thickness Formation Main thickness 20 hours layer in tape resistance No. Substrate Type (g/m.sup.2) (mass %) Type (m) method component (nm) (A/cm.sup.2) removal test after 20 hours Adhesion Remarks 1 SUS447J1 N/A Au 1.0 Plating 0.041 Peeled Pass Fail Comparative Example 2 Ni 0.02 1.0 0.045 Not peeled Pass Pass Example 3 0.02 3.0 0.041 Not peeled Pass Pass Example 4 0.19 1.0 0.049 Not peeled Pass Pass Example 5 0.75 1.0 0.119 Not peeled Pass Pass Example 6 0.75 5.0 0.068 Not peeled Pass Pass Example 7 Ni-P 0.001 12 1.0 0.043 Not peeled Pass Pass Example 8 0.001 12 3.0 0.040 Not peeled Pass Pass Example 9 0.03 15 0.5 0.063 Not peeled Pass Pass Example 10 0.03 15 1.0 0.047 Not peeled Pass Pass Example 11 0.42 15 1.0 0.095 Not peeled Pass Pass Example 12 1.4 16 1.0 0.295 Not peeled Fail Pass Comparative Example 13 1.5 16 3.0 0.273 Not peeled Fail Pass Comparative Example 14 2.0 15 5.0 0.330 Not peeled Fail Pass Comparative Example 15 Cu 0.2 1.0 0.045 Not peeled Pass Pass Example 16 Ag 0.5 1.0 0.086 Not peeled Pass Pass Example 17 Ni 0.01 Carbon 10.0 Firing after 0.130 Not peeled Pass Pass Example 18 Ag 0.005 black-dispersed 5.0 application 0.165 Not peeled Pass Pass Example 19 1.2 epoxy resin 5.0 0.314 Not peeled Fail Pass Comparative Example 20 SUS447JI N/A Graphite 3.0 Firing after 0.175 Peeled Pass Fail Comparative Example 21 Ni-P 0.007 12 dispersed 5.0 application 0.184 Not peeled Pass Pass Example 22 1.5 15 phenol resin 5.0 0.467 Not peeled Fail Pass Comparative Example 23 Ni 0.002 Diamond-like 0.3 CVD 0.174 Not peeled Pass Pass Example 24 1.3 carbon 1.0 0.391 Not peeled Fail Pass Comparative Example 25 Ni-P 0.01 15 Ni.sub.3Sn.sub.2 1.0 Plating 0.022 Not peeled Pass Pass Example 26 1.5 16 3.0 0.338 Not peeled Fail Pass Comparative Example 27 Ni-P 0.01 15 TiN-dispersed 2.0 Plating 0.080 Not peeled Pass Pass Example 28 1.5 15 Ni.sub.3Sn.sub.2 5.0 0.395 Not peeled Fail Pass Comparative Example 29 Ni-P 0.01 15 Ni.sub.3Sn.sub.2 1.0 Plating SnO.sub.2 15 0.013 Not peeled Pass Pass Example (excellent) 30 Ni-P 0.01 15 SnO.sub.2 0.1 PVD 0.003 Not peeled Pass Pass Example (excellent) 31 1.5 16 0.1 0.275 Not peeled Fail Pass Comparative Example 32 Au 0.003 TiO.sub.2 0.1 PVD 0.004 Not peeled Pass Pass Example (excellent) 33 Ni 0.005 TN 0.1 PVD 0.168 Not peeled Pass Pass Example 34 1.5 0.1 0.429 Not peeled Fail Pass Comparative Example 35 Ni 0.005 Polyaniline 1.0 Electropoly- 0.138 Not peeled Pass Pass Example 36 1.2 1.0 merization 0.304 Not peeled Fail Pass Comparative Example 37 Titanium Ni 0.01 Au 1.0 Plating 0.037 Not peeled Pass Pass Example 38 JIS 1 type 1.4 1.0 0.237 Not peeled Fail Pass Comparative Example

[0176] The table reveals the following points.

[0177] (a) The samples of Examples all had low current density after 20 hours in the corrosion resistance evaluation, and had favorable corrosion resistance even in the event of long exposure to high potential as in the separator use environment. In particular, Nos. 29, 30, and 32 had excellent corrosion resistance. Moreover, the samples of Examples all had excellent adhesion property.

[0178] (b) The samples of Comparative Examples Nos. 1 and 20 with no strike layer did not have desired adhesion property.

[0179] (c) The samples of Comparative Examples Nos. 12 to 14, 19, 22, 24, 26, 28, 31, 34, 36, and 38 with the coating weight of the strike layer exceeding the appropriate range had high current density after 20 hours in the corrosion resistance evaluation, and did not have desired corrosion resistance.

REFERENCE SIGNS LIST

[0180] 1 membrane-electrode joined body [0181] 2, 3 gas diffusion layer [0182] 4, 5 separator [0183] 6 air passage [0184] 7 hydrogen passage