JP5120799B2 - Separator for polymer electrolyte fuel cell and method for producing stainless steel used therefor - Google Patents

Description

  The present invention is an austenitic stainless steel excellent in corrosion resistance under an environment exposed to a strong acid in a separator sandwiching a solid polymer electrolyte membrane in a fuel cell and a stainless steel used therein, and is used as a current-carrying component. In particular, the present invention relates to a metal material suitable for a base material stainless steel for a separator of a polymer electrolyte fuel cell.

Among the fuel cells, the polymer electrolyte fuel cell operates at a low operating temperature of 60 to 100 ° C., so that it is easy to start and stop, has a short start-up time, and is small and light and has a high output density. And so on. Therefore, for example, it is expected to be put to practical use as a small power supply for home use that uses city gas as a fuel, and a power supply for use in a low-pollution electric vehicle that uses hydrogen gas, methanol, or gasoline as fuel.
The polymer electrolyte fuel cell utilizes the fact that a solid polymer resin having a proton exchange group in the molecule functions as a proton conductive electrolyte. Like other types of fuel cells, the polymer electrolyte fuel cell A fuel gas such as hydrogen is allowed to flow on one side of the membrane and an oxidizing gas such as air is allowed to flow on the other side.

  1 and 2 show the structure of a polymer electrolyte fuel cell. FIG. 1 is an exploded configuration diagram of a single cell (1) of a fuel cell, in which a fuel electrode membrane (anode) (3) is disposed on one surface of a solid polymer electrolyte membrane (2) and the other surface. Is provided with an oxidant electrode film (cathode) (4). Each electrode (3) and (4) carries an anode catalyst layer (3a) and a cathode catalyst layer (4a) on the surface side of the solid polymer electrolyte membrane (2). Separators (6) and (7) are disposed on both sides of the membrane electrode assembly (MEA) (5) thus configured. Then, as shown in FIG. 2, several tens to several hundreds of the single cells (1) are stacked, and current collecting plates (8) and (9) are arranged on both sides of the obtained stack. Since the amount of power generation per cell is very small, it can be taken out by stacking a large number of cells with the solid polymer electrolyte membrane (2) sandwiched between the separators (6) and (7) as one unit. The amount of electric power is increased.

A typical example of the solid polymer electrolyte membrane (2) is a fluorine-based exchange resin membrane having a hydrogen ion (proton) exchange group. Each of the anode catalyst layer (3a) and the cathode catalyst layer (4a) is supported in a highly dispersed manner comprising a particulate platinum catalyst, graphite powder, and, if necessary, a fluororesin having hydrogen ion (proton) exchange groups. The catalyst is used and is configured to contact the fuel gas (10) or the oxidizing gas (11). The fuel gas (10) is caused to flow through a flow path (6a) provided in the separator (6), and hydrogen is supplied to the fuel electrode film (anode) (3). On the other hand, the oxidizing gas (11) is caused to flow through the flow path (7a) provided in the separator (7), and oxygen is supplied to the oxidant electrode film (cathode) (4). Hydrogen or a hydrogen-containing gas is used as the fuel gas (10), and an oxygen gas-containing gas such as air is used as the oxidizing gas (11).
The gas supplied in this manner causes the following electrochemical reaction to generate DC power.
Anode: H ₂ → 2H ⁺ + 2e (1)
Cathode: 2H ⁺ + 1 / 2O ₂ + 2e → H ₂ O (2)
Total battery reaction: H ₂ + 1 / 2O ₂ = H ₂ O (3)
The constituent materials of the separator mainly used so far can be divided into a carbon resin mold separator, an expanded graphite mold separator, and a metal separator. Each of these separators is long and short.

  As the material used for the separator, a carbon plate is used because the surface is exposed to a strong acid, and in addition to being a material that can withstand this, it is necessary to have good conductivity. However, the carbon plate is subjected to gas impervious treatment, and a groove is formed on the plate surface to form a gas flow path. However, in order to avoid expensive cutting for that purpose, there is a method of forming a gas flow path by compressing or injection molding a resin kneaded with graphite powder, but the moldability is increased by increasing the amount of the kneaded resin. When improved, the electrical resistance increases, while reducing the electrical resistance by reducing the thickness of the separator decreases the mechanical strength.

  On the other hand, durability improves by using stainless steel for a separator. Metal separators are attracting attention for the purpose of cost reduction. As the metal separator, metal materials such as titanium and stainless steel have been studied, but titanium has a high material cost. On the other hand, stainless steel is a relatively inexpensive material, and due to the presence of a passive film formed on the surface, relatively good corrosion resistance is exhibited in the use environment as a separator. However, since corrosion resistance is inferior to carbon materials and contact resistance generally increases, research on contact surfaces is being improved. In addition, stainless steel has a problem that the life of the battery is shortened due to deterioration of the performance of the polymer electrolyte membrane due to the eluted metal ions.

  Examples of stainless steel separators that have been studied include stainless steel based on SUS316 (main component composition: Fe-13Ni-17Cr-2Mo). For example, Table 1 (see “steel type: f” of the test material) in Examples of Japanese Patent Application Laid-Open No. 2002-151111 (Patent Document 1) includes a material containing 0.72% by mass of Cu in SUS316L. . However, when the inventors of the present invention conducted a test under severe corrosion conditions on SUS316L stainless steel, it was found that the corrosion resistance was not sufficient.

JP 2002-151111 A

  In view of the above-mentioned present situation, while taking advantage of the above-mentioned stainless steel separator, it is an object to develop stainless steel whose acid resistance is markedly improved compared to conventional materials, and by solving this, solid polymer It is an object of the present invention to contribute to improving the durability of the fuel cell and to improving its performance.

  The present invention does not substantially contain nickel, and by making austenitic stainless steel by adding a high concentration of nitrogen, the corrosion resistance is greatly improved, and plastic workability is ensured, and non-metallic inclusions are added. It has been found that by creating a stainless steel with a reduced starting point of corrosion by defining a component composition to be reduced and making it a clean steel, it can be advantageously used as a separator for polymer fuel cells with excellent acid resistance. by.

The separator of the polymer electrolyte fuel cell according to the first invention of the present application has a chemical component composition (unit: mass%),
0 <C ≦ 0.08
0 ≦ Si ≦ 0.50
0 ≦ Mn ≦ 0.30
P ≦ 0.020
S ≦ 0.002
O ≦ 0.005
19.0 ≦ Cr ≦ 28.0
Ni ≦ 0.01
1.0 ≦ Mo ≦ 3.0 and 1.00 <N ≦ 2.00
And
Furthermore, 0 ≦ Ca <0.0050 and 0.0005 ≦ sol. Containing at least one of Al ≦ 0.020,
It is characterized in that the balance is stainless steel made of Fe and inevitable impurities.

The separator of the polymer electrolyte fuel cell according to the second invention of the present application is the first invention, wherein the contents of C, Si, Mn, O and Ni are
0 <C ≦ 0.03
0 ≦ Si ≦ 0.30
0 ≦ Mn ≦ 0.10
O ≦ 0.003
Ni ≦ 0.005
It is characterized by satisfying

  3rd invention of this application is a manufacturing method of stainless steel used for a separator of the 1st or 2nd invention, and after hot-forging a steel ingot of stainless steel, it is hot-rolled, The obtained hot rolled stainless steel sheet is subjected to a complete annealing treatment and at least pickled.

  According to the present invention, the acid content is improved by making the N content high without substantially containing Ni, and at the same time, the oxygen is reduced by appropriate combined deoxidation of Al and Ca as main deoxidizer elements. And high purity stainless steel with reduced non-metallic inclusions by sufficiently reducing sulfur content by desulfurization treatment, and austenitic stainless steel with high concentration of N despite being Ni-free Thus, by improving the plastic workability, it becomes possible to provide stainless steel having acid resistance and corrosion resistance that can withstand the use environment of the separator of the polymer electrolyte fuel cell. As a result, the corrosion resistance of the stainless steel separator is improved, and the remarkable improvement in acid resistance improves the performance deterioration of the polymer electrolyte membrane due to elution of metal ions, contributing to the extension of the battery life and industrially beneficial effects. Is brought about.

Hereinafter, the present invention will be described in detail and preferred embodiments of the present invention will be described.
As a method for melting a steel ingot having the chemical composition of stainless steel of the present invention, an electroslagrimelting (hereinafter abbreviated as “ESR”) method can be used to increase the melting atmosphere to 1 atmosphere or more. It is desirable to use the pressure type ESR method. This is to add a high N content and to prepare clean stainless steel. And as a chemical component which should comprise the stainless steel of this invention, in addition to C, Si, Mn, Cr, Mo and N, the predetermined content of at least 1 sort of chemical component in Ca and Al is required. .

  However, Si and Mn may be substantially 0% by mass. Moreover, Ca content and sol. Regarding the relationship with the Al content, see sol. If the Al content is 0.0005 mass% or more, the Ca content may be substantially 0 mass%. On the other hand, if the Ca content exceeds 0% by mass, sol. The Al content may be substantially 0% by mass. Here, the content of Ca or sol. The fact that the Al content is substantially 0% by mass refers to a case where it is recognized as a so-called trace in ordinary steel analysis. By adopting the ESR method as a method for melting steel ingots, sufficient deoxidation of the molten steel and sufficient separation of oxide-based nonmetallic inclusions in the molten steel into slag phases are performed. This is because good cleanliness is achieved for the non-metallic inclusions.

  On the other hand, Ni is not a necessary constituent element in the present invention, and the smaller the better, and P, S, and O, which are inevitable elements common to steel, limit the upper limit to a low content as described later.

Hereinafter, the reason why the chemical component composition in the present invention is limited as described in the inventions according to claims 1 and 2 will be described.
C: 0.08 mass% or less (however, 0 mass% is not included)
C contributes to improving the strength of the steel and is effective as an austenite-forming element, but on the other hand, it is an element that impairs the corrosion resistance and toughness of the steel. And from the viewpoint of securing toughness, the content should be reduced as much as possible. And even if C content is substantially 0 mass%, the stainless steel which this invention aims at can be achieved by satisfy | filling the other chemical component composition described below. However, in order to make the C content substantially 0% by mass, the cost of the raw material for electrode preparation in ESR is remarkably high, so that it is not practically a good idea. Therefore, in the stainless steel according to the present invention, the C content does not include 0% by mass. And in order to ensure the material characteristic in this invention to a high level, and when the manufacturability of the stainless steel in a steelmaking process is considered, C content should accept | permit an upper limit to 0.08 mass%. However, in consideration of cold plastic working a stainless steel plate into a separator shape, it is desirable that C is as low as possible, so that the upper limit is more preferably 0.03% by mass.
Si (silicon): 0.50 mass% or less (including 0 mass%)

Si is an element that acts as a deoxidizing agent. On the other hand, Si generates SiO ₂ which is a deoxidation product, which promotes the generation and growth of oxide-based nonmetallic inclusions. It causes a decline. Moreover, since Si reduces the ductility of the material, it should be kept low. Further, since Si promotes the formation of a delta ferrite phase exhibiting magnetism, it should be suppressed to a low value from the viewpoint of preventing this. On the other hand, in order to ensure the deoxidizing ability, an appropriate amount of Ca and / or Al is added as another deoxidizing element, which is combined with the separation and removal action of oxide-based nonmetallic inclusions into the slag phase in the ESR process. Therefore, it was decided to significantly reduce the amount of oxide-based nonmetallic inclusions in steel. In addition, considering the manufacturability, the upper limit value of the Si content was set to 0.50% by mass. And in the present invention, it is a melting process called ESR, and as will be described later, since melting and refining are performed in an N atmosphere at a predetermined pressure, as long as the deoxidation operation with Ca and / or Al is appropriately performed. Even if the Si content is substantially 0% by mass, sufficient deoxidation can be performed. However, the addition of Al to the molten steel is completed before the preparation of the ESR consumable electrode ingot, but the addition of Ca to the molten steel should be performed during the melting and refining in ESR, which is a non-oxidizing atmosphere. To finish deoxidation and to ensure improved cleanliness of the ESR steel ingot. Therefore, the Si content may be 0% by mass. As long as the Ca and / or Al content is within the scope of the present invention, the Si content is more preferably 0.30% by mass or less from the viewpoint of reducing the amount of oxide-based nonmetallic inclusions.

In the present invention, as described above, the N content is limited to an extremely high content exceeding 1.0% by mass and 2.0% by mass or less compared to the N content in the stainless steel of the conventional example. Therefore, an improved pressure-type ESR method (to be described later, the same applies hereinafter) created by the inventors of the present invention, which will be described later, does not use an additive source material containing Si, such as silicon nitride, as a N additive source. with an alloy or a chromium nitride or the like, a nitrogen gas up to a pressure of smelting atmosphere in ESR and 5 MPa, by the use of CaF ₂ plain system as and additive slag components, separation of nonmetallic inclusions from the molten metal to the slag In addition, the Si content was advantageously controlled by limiting the source of Si contamination in the molten metal. Accordingly, the Si content is limited to 0.50% by mass or less (including 0% by mass), and more desirably 0.30% by mass or less (including 0% by mass).
Mn: 0.30 mass% or less (including 0 mass%)
Mn is an element that acts as a deoxidizing agent like Si, and contributes to stabilization of the austenite phase. Furthermore, since Mn increases the solubility of N in the molten metal, it is generally an extremely effective element for producing high-N steel.

In the present invention, the N content is limited to a high value of more than 1.0% by mass and not more than 2.0% by mass, and from this viewpoint, positively containing Mn is very advantageous at first glance. . However, when the Mn content is increased, the deoxidation product, MnO, promotes the formation and growth of oxide-based non-metallic inclusions in accordance with the increase in the Si content. Corrosion resistance decreases and toughness also decreases.
Therefore, in the present invention, it was noted that the Mn content should be as low as possible. This attention is one of the remarkable features of the present invention. In the present invention, with respect to the deoxidation action of Mn, in the same manner as Si, in order to ensure the deoxidation ability even if the addition amount is limited, any one of Al and Ca or Al and Ca in appropriate amounts. This is to reduce the dissolved oxygen in the molten metal to a very low value.

By adopting such a controlled deoxidation method, it becomes possible to further reduce the content of Mn which originally has a deoxidation function, and is 0.30% by mass or less.
Desirably, the Mn content can be less than 0.10% by mass. By doing so, the amount of non-metallic inclusions containing Mn-based oxides can be further reduced, and the morphological dimensions can be reduced. Therefore, it is extremely effective for improving the corrosion resistance of the steel of the present invention and the steel material.
As a further countermeasure against oxide-based non-metallic inclusions, as described above with respect to the Si content, melting and refining are performed by an improved pressure ESR method under appropriate conditions (this improved addition). A more detailed description of suitable melting and refining conditions for the pressure type ESR method will be described later).

Note that N addition in stainless steel greatly contributes to stabilization of the austenite phase. Thus, in the present invention, from the viewpoint of improving the corrosion resistance and toughness described above, considering the manufacturability in the improved pressurized ESR process, particularly the stable preparation on the components and supply of the consumable electrode, the Mn content is reduced to 0. It was 30 mass% or less. Here, the lower limit value of the Mn content is the ESR process in the present invention, as in the case of the Si content, and, as will be described later, an N atmosphere at a predetermined pressure (and hence a non-oxidizing atmosphere). Therefore, as long as the Ca and / or Al deoxidation operation is appropriately performed, sufficient deoxidation can be performed even if the Mn content is substantially 0% by mass. In addition, it is possible to perform sufficient deoxidation by an appropriate amount of Al addition deoxidation, to suppress the generation of Al ₂ O ₃ -containing inclusions, and to extremely reduce the residual amount.

On the other hand, in order to suppress the production amount of MnS, the Mn content is set as low as possible, and more desirably, by specifying the S content to less than 0.002% by mass, as described later, A synergistic effect is also obtained in that the amount of MnS inclusions generated can be further reduced.
Accordingly, the Mn content may be 0% by mass. As described above, the Mn content is limited to 0.30% by mass or less (including 0% by mass), and desirably 0.10% by mass or less (including 0% by mass).

  In the present invention, in order to produce stainless steel having further excellent corrosion resistance, strength and formability or a separator using this stainless steel, the contents of P, S and O as inevitable impurities are as follows. limit.

P: 0.020% by mass or less P segregates at the crystal grain boundary, easily lowers corrosion resistance, and lowers toughness. Therefore, it is desirable that the content is small. However, since reduction more than necessary causes an increase in cost, the upper limit is allowed to 0.020% by mass in consideration of manufacturability.

S: 0.002 mass% or less S reduces corrosion resistance and hot workability. In this invention, Mn content is prescribed | regulated to 0.30 mass% or less, and in order to reduce the production | generation amount of a MnS type nonmetallic inclusion, it is desirable to reduce S content as much as possible. Moreover, it is also possible to reduce the generation of CrS-based non-metallic inclusions, and it is desirable to reduce the S content as much as possible in order to improve corrosion resistance. However, if the S content is limited to an extremely low level, the desulfurization cost increases greatly, so the upper limit is allowed to 0.002% by mass.
O (oxygen): 0.005 mass% or less O contributes to the formation and growth of oxide-based nonmetallic inclusions and causes a decrease in corrosion resistance. Therefore, it is desirable to reduce the content thereof as much as possible. However, manufacturability must also be considered, and the upper limit of the O content is allowed to 0.005 mass%. However, from the viewpoint of reducing corrosion resistance, it is desirable that the content be 0.003% by mass or less.

Cr: 19.0-28.0 mass%
Cr is an element that is fundamentally necessary for ensuring corrosion resistance in stainless steel, and a Cr content of 19% by mass or more is required to form a passive film enriched with Cr by acid immersion. As the Cr content increases, the contact resistance is stabilized, and the acid resistance in an acidic atmosphere is also improved. The stainless steel according to the present invention is defined as the chemical composition of the austenitic stainless steel. The reason is that austenitic stainless steel is superior in plastic workability compared to ferritic steel, and is therefore advantageous for forming into a groove shape or the like when processing a separator by press working. However, Cr is also a ferrite-forming element, and if it is excessively contained, intermetallic compounds such as the σ phase are likely to precipitate, resulting in embrittlement of the steel. Therefore, the Cr content is 28.0% by mass or less. On the other hand, the present inventors, in the case where the chemical component composition other than Cr is within the scope of the present invention, by defining the Cr content in the range of 20.0 mass% or more and 25.0 mass% or less, As a mechanical property of the thin steel plate after the solution treatment, it has been found that the elongation and drawing are remarkably improved in a state where the strength is sufficiently secured (Japanese Patent Application No. 2006-197418). Therefore, the range of the Cr content in the present invention is limited to 19.0 to 28.0% by mass, and more preferably within the range of 20 to 25% by mass.

Ni (nickel): 0.01% by mass or less Since Ni is an austenite-forming element, it contributes to stabilization of the austenite phase, and Ni is also effective in improving corrosion resistance.
On the other hand, the inventors of the present application pay attention to the action of improving the corrosion resistance of N in view of Cr% + 3Mo% + 10N%, which is known as the corrosion resistance index. As a result of Ni elution test from stainless steel at an assumed pH of 2.8, a hint was obtained that Ni-free high-N content austenitic stainless steel obtained good results (see Japanese Patent Application No. 2006-197418). The austenitic stainless steel was prepared by reducing the Ni content as much as possible and by increasing the N content. The concentration which does not substantially contain Ni is 0.01% by mass or less, preferably 0.005% by mass.

Mo: 1.0-3.0 mass%
Mo is an element that contributes to improving the corrosion resistance of stainless steel together with Cr, and in particular, the effect of improving the pitting corrosion resistance can be obtained by addition of 1.0 mass% or more of Mo. The effect of improving the pitting corrosion resistance of Mo becomes effective by coexistence with Cr. As the Cr content increases, a larger amount of Mo can be added. However, as the content increases, the material is hardened and the workability of the material is lowered. Therefore, the upper limit of the Mo content is set to 3.0% by mass.

N: more than 1.00% by mass to 2.00% by mass
N is effective for improving the corrosion resistance and also plays a large role as an austenite-forming element. In the chemical component composition of the present invention, the lower limit of the N content should exceed 1.00% by mass in order to stabilize the austenite crystal structure. On the other hand, increasing the N content also contributes to improving the strength. However, when the N content exceeds 2.00% by mass, the formation of Cr nitride is particularly promoted, and the corrosion resistance decreases due to the decrease in the Cr oxide film due to the decrease in the Cr content. Also, toughness is reduced. Accordingly, the N content is limited to a range of more than 1.00% by mass to 2.00% by mass or less.
Next, Ca and Al need to contain either one or both. However, the Al content is sol. From the viewpoint of effective deoxidizing element concentration. Al content.

Ca: less than 0.0050% by mass Ca is effective as a deoxidizing agent and a desulfurizing agent. Therefore, it contributes to the reduction of non-metallic inclusions and to the improvement of corrosion resistance and toughness. However, in the present invention, since the S content is regulated to 0.002% by mass or less as described above, it is defined mainly from the viewpoint of a deoxidizing element. According to the improved pressurization type ESR process in the present invention, the Ca content is deoxidation and desulfurization effect even if the Ca content of the ESR steel ingot is less than 0.0050 mass% due to Ca deoxidation in ESR. Is fully demonstrated. On the other hand, the lower limit value of the Ca content is not particularly limited. The analysis value may be 0% by mass. The reason is that, considering the detection limit and accuracy of quantitative analysis of Ca, when the Ca content is extremely low, the analysis value is determined as a so-called trace, and the Ca content is described as 0 ppm. It is possible. The stainless steel according to the present invention has a very low O content and a very good cleanliness in the case where the measured value in the steel analysis in the state where a small amount of Ca is present is a so-called trace. It is because it does not exclude.
On the other hand, excessive addition of Ca leads to the formation of CaN precipitates and an increase in the residual amount of non-metallic inclusions, resulting in deterioration of corrosion resistance. Therefore, in order to prevent these, the upper limit of Ca content is set to 0. It should be limited to .0050% by weight.

Al: 0.0005 to 0.020 mass%
In the ESR of the stainless steel manufacturing process according to the present invention, the main part of the consumable electrode (the base part of the consumable electrode) is previously melted in molten steel having a predetermined composition in a melting refining furnace and solidified. Provide the steel ingot. In the process up to the preparation of the steel ingot, at least Al is used as a deoxidizer in the molten steel to reduce oxide-based nonmetallic inclusions. The sol. As the Al content, about 0.010 to 0.050% by mass is required, and as a clean steel ingot manufactured by ESR using this, the sol. It should contain at least 0.0005% by mass of Al. On the other hand, in order to obtain a sufficiently clean stainless steel ingot by separating the nonmetallic inclusions into the slag phase by ESR, sol. The upper limit of the Al content should be 0.020% by mass.

The chemical component composition of the stainless steel according to the present invention is within the above-mentioned range including the regulation values of P, S and O as inevitable chemical components.
For the purpose of producing an austenitic stainless steel having a corrosion resistance higher than that of the separator having the above chemical composition as a base material for a separator of a polymer electrolyte fuel cell, for example, 4% by mass in a range where W is not excessive. It may be added in the following. Moreover, when manufacturing a separator, when cutting is involved, for example, 0.05% by mass or more of Cu may be contained for the purpose of improving machinability. However, since excessive addition of Cu impairs hot workability, it should desirably be 1.0% by mass or less.

As a method for melting the stainless steel according to the present invention, in the improved pressurization type ESR method, in particular, an addition method for obtaining a high N content stainless steel and a Ca-based deoxidation for melting a high clean steel The method is important. For that purpose, for example, the improved ESR operation created as follows may be performed.
First, a plurality of grooves having a predetermined depth and width are formed in the vertical direction on the outer peripheral portion of the cylindrical consumable base electrode, and a predetermined weight is provided along the groove in the predetermined groove. Then, the following steel pipe containing the N addition source is set so as to be fitted in each groove. That is, for example, ferrochromium nitride (FeCrN) powder is vacuum sealed and sealed at a predetermined packing density as a N addition source to a stainless steel pipe having a predetermined component, and sintered at about 900 ° C. in a vacuum furnace. Is prepared and set in the groove. The N-added source containing pipe set in this way is joined and fixed to the consumable base electrode by welding to prepare a nitrogen-added consumable electrode for ESR. However, the amount of the ferrochrome nitride powder enclosed in the pipe and the chemical composition of the consumable base electrode are appropriately adjusted in consideration of the chemical composition of the ESR steel ingot to be melted, and pressurized ESR. The melting and refining atmosphere is adjusted to a nitrogen gas atmosphere at an appropriate pressure within a range of, for example, about 0.1 to 5 MPa. In addition, since the Ca wire dissolves in a nitrogen atmosphere during the melting and refining period of the electrode, it is prevented from being oxidized by the atmosphere and contributes to the deoxidation reaction while being gradually added to the molten metal.

On the other hand, as the ESR slag, for example, a CaF ₂ plain system is used as the added slag. This facilitates the separation of non-metallic inclusions from the molten metal into the slag, and restricts the source of Si mixing into the molten metal, making it advantageous to control the upper limit of the Si content. The SiO ₂ component is not added to facilitate adjustment of the Si content of the ESR steel ingot, and the Al ₂ O ₃ component is not added to adjust the Al content of the ESR steel ingot.
The ESR steel ingot having the desired chemical component composition can be melted by appropriately operating the pressurized ESR apparatus under such conditions. The N addition source material is not limited to ferrochromium nitride (FeCrN), and may be inorganic nitrogen such as chromium nitride (CrN). However, in order to avoid mixing of Mn and Si, ferromanganese nitride (FeMnN) and silicon nitride (SiN) containing at least any element are not used.

A desirable processing method for forming from the highly purified ESR stainless steel ingot having the chemical composition of the present invention thus obtained to the separator of the polymer electrolyte fuel cell will be described. After the ESR steel ingot is processed into a slab shape by hot forging, it is hot-rolled into a steel plate. The obtained hot-rolled stainless steel plate is fully annealed, pickled, and then pressed into a separator. There is a method of processing.
Therefore, as the stainless steel according to the present invention, a stainless steel plate obtained by completely annealing a hot-rolled material is desirable as a separator material.

By the way, in general, austenitic stainless steel is obtained by adding an element having an action of stabilizing the austenitic structure to ferritic stainless steel having excellent corrosion resistance, and varies depending on the chemical composition of the obtained stainless steel. After sufficiently heating at a predetermined temperature between about 1010 to 1180 ° C. and then rapidly cooling, it is produced by dissolving the contained carbide into the austenitic structure, whereby the austenitic stainless steel has excellent corrosion resistance. It is equipped. The mechanical properties of austenitic stainless steel are generally determined after heating the steel to a temperature above the temperature at which the alloy components of the steel dissolve in the solid solution, maintaining a sufficient amount of time, and quenching to prevent precipitation. It evaluates by the test value obtained about the test piece after performing a chemical conversion treatment.
As for the austenitic stainless steel of the present invention, grasping the level of the mechanical property value after the solution treatment of the hot-rolled steel sheet is useful for estimating the press formability evaluation of the separator steel sheet. Therefore, in the examples, the level value of the mechanical property value by the tensile test after the solution treatment of the hot-rolled steel sheet was also tested.

The present invention will be described in detail based on examples. Table 1 shows examples of separator stainless steels for polymer electrolyte fuel cells that fall within the scope of the present invention, and separator stainless steels for polymer electrolyte fuel cells that fall outside the scope of the present invention. Each chemical component composition is shown about the comparative example as steel.
The stainless steel having the component composition of “Example” in Table 1 was subjected to both a metal elution test and a power generation test described later.
On the other hand, the stainless steel having the component composition of “Comparative Example 1” was subjected to a metal elution test, and the stainless steel having the component composition of “Comparative Example 2” was subjected to a power generation test.

  In Table 1, the content of Al is “no analysis value” because deoxidation with Al is performed in the process of melting the consumable base electrode 2 of FIGS. 3 and 4. Al is contained, but in the melting stage of the ESR steel ingot of this example, Al for deoxidation of Al may not be added to the nitrogen-added consumable electrode 1 of FIGS. 3 and 4. Yes, meaning that Al analysis is not performed. On the other hand, “no analytical value” of the Al content in Comparative Examples 1 and 2 is generally contained because deoxidation is performed with Al in the ingot stage of the steel ingot or slab. Since JIS does not define the Al content, it means that Al analysis is not performed.

1. [Method for Preparing Sample Material for Examples]
(1) Method for melting steel ingots of test materials for examples

First, a stainless steel ingot having the chemical composition of the examples belonging to the scope of the present invention was melted by the improved pressure ESR method described below. The chemical component composition of the ESR steel ingot is as shown in the examples of Table 1, and the details of the melting method are as follows.
In order to melt a high-N content austenitic stainless steel with excellent N N content and cleanliness of non-metallic inclusions, which is a component characteristic of the ESR steel ingot of the example, conventional pressure-type ESR by enhancing the breakdown voltage capability of the ambient pressure mechanism, ability of melting and refining reaction and ESR body shell in the apparatus, N ₂ gas atmosphere pressure of melting and refining period, adjusted in the range of about 0.1~5MPa A modified device was used. A nitrogen-added consumable electrode, which is an improved consumable electrode manufactured in the following process, is set as an ESR consumable electrode, and a CaF ₂ -CaO two-component premelt slag is used as the slag. Remelting and refining using an additive type consumable electrode as a melting material, Ni-free, ultra-low Mn, ultra-high N, and non-metal with 100 mmφ × about 320 mm height having the target chemical composition of this example A highly clean 20 kg ESR ingot was melted for inclusions.

At that time, as a basic operation for adjusting the N content of the ESR steel ingot to the ultrahigh level of the target value, (1) N contained in the nitrogen additive fixed to the surface layer of the nitrogen-added consumable electrode It was performed by maintaining the symmetry of the content and the nitrogen additive distribution of the electrode surface layer, (2) controlling the N ₂ gas atmosphere pressure during the melting and refining period, and (3) controlling the melting and refining temperature.
Moreover, the strong deoxidation by the metal Ca main body of the molten metal was employ | adopted for the basic method of highly purified steel melting. In addition, Ca addition amount is prepared by mounting an appropriate amount with respect to the weight of the consumable electrode by incorporating a metal Ca wire into the consumable electrode. Further, regarding the component composition of the molten slag, the oxygen and sulfur potential of the slag By optimizing the extremely low flow and fluidity, the flotation and separation removal of the deoxidized product and desulfurized product from the molten (molten steel) bulk or droplets to the molten slag phase is promoted and the reoxidation of the molten bulk is prevented. planned. Ca was also subjected to desulfurization at the same time.

  Here, the manufacturing process of the above-mentioned nitrogen addition type consumable electrode used as the raw material of the ESR steel ingot for Example and its properties and form are described. The nitrogen-added consumable electrode has properties and forms effective for adjusting the N content to a desired content level among the components of the ESR steel ingot to be melted. FIG. 3 is a schematic perspective view of a nitrogen-added consumable electrode for explaining the Ca addition method, and FIG. 4 is a horizontal sectional view thereof.

The nitrogen-added consumable electrode 1 was manufactured as follows. A plurality of grooves 3 (eight in the figure) are formed in the longitudinal direction of the outer peripheral portion of the cylindrical consumable base electrode 2, and a metal Ca wire 5 is first inserted into the grooves 3 along the grooves 3. Furthermore, the metal Ca wire 5 is pressed from the outside with a cylindrical nitrogen additive 4 and fitted into the groove 3, and the nitrogen additive 4 is fixed to the consumable base electrode 2 by welding. Set up and united.
In the above, the consumable base electrode 2 corresponds to a main raw material for melting an ESR steel ingot, and was prepared from a steel ingot with good cleanliness melted in a vacuum induction melting furnace. The chemical composition of the steel ingot is substantially Ni in consideration of the nitrogen additive 4, the metal Ca wire 5, the slag composition, the nitrogen atmosphere pressure during melting, and the like with respect to the target chemical composition of the ESR steel ingot to be melted. The chemical component composition was not included.
Also, the nitrogen additive 4 shown in FIG. 4 has a structure in which a chromium nitride (CrN) powder is vacuum-filled and sealed in a stainless steel pipe 6 and vacuum-sintered (a chromium nitride powder is sintered). (Conjugation) 7 is shown.

The method for preparing the nitrogen additive 4 will be further described. Using a fine powder (particle size: 5 μm or less) of chromium nitride (CrN) powder (N content: 20 mass%) as a nitrogen addition source material, one end of a SUS403 stainless steel pipe 6 having a predetermined size is sealed, The other end of the pipe was sealed by welding while reducing the pressure to 10 ⁻³ torr or less and holding it at a filling density of 3.2 g / cm ³ . Next, chromium nitride was sintered at 900 ° C. in the vacuum furnace of the preparation thus obtained to prepare a nitrogen additive 4. The nitrogen-added body 4 filled with a chromium nitride sintered body 7 is formed on the outer peripheral portion of a 65 mmφ consumable base electrode 2 with a groove 3 prepared in advance. The nitrogen-added consumable electrode 1 was manufactured by attaching each of the plurality of grooves 3 as described above.
In the above nitrogen-added consumable electrode 1, the setting of the chemical component composition of the consumable base electrode 2, the selection of the chemical component composition and dimensions of the SUS403 stainless steel pipe, and the number of fixed nitrogen-added bodies 4 are as follows. It determined appropriately so that the ESR steel ingot which has the target chemical component composition of the stainless steel for Examples which belongs in the range can be melted.

  The steel ingot having the chemical composition of the examples shown in Table 1 melted by the ESR method as described above is hot forged, and then hot rolled to obtain a plate thickness of 15 mm and a plate width: A 70 mm hot-rolled plate was applied, and after the solution treatment, the scale was removed, and then the thickness was reduced by mechanical cutting to finish a plate having a thickness of 5.0 mm. The specimens thus obtained were subjected to (a) metal dissolution test and (b) power generation test.

  Of the chemical components of the plate cut and finished to a thickness of 5.0 mm, at least the chemical components shown in Table 1 have the same composition as that of the ESR steel ingot shown in Table 1, and the above processing And it can be considered that there is no change in the heat treatment process.

2. [Method for preparing test material for comparative example]
(A) For the metal elution test, a commercially available cold-rolled stainless steel plate having a thickness of 1.0 mm belonging to the known SUS316L component belonging to the austenitic stainless steel of Comparative Example 1 shown in Table 1 was obtained. After heating at 1230 ° C. for 15 minutes, it was cooled with water and subjected to a solution treatment to obtain a test material.
(B) For a power generation test, obtain a commercially available hot rolled stainless steel plate having a thickness of 6.0 mm belonging to a known SUS304 component belonging to the austenitic stainless steel shown in Comparative Example 2 in Table 1, A test material was used.

[Accuracy test method]
In order to test important characteristic values when using the stainless steel according to the present invention as a material for a separator for a polymer electrolyte fuel cell, (1) Corrosion A metal elution test in the environment and (2) a power generation test using a single cell of the fuel cell were performed. The method of each accuracy test and the results obtained are as follows.

(1) Metal dissolution test method and test results A metal dissolution test was performed as follows. For the examples, the above-mentioned hot-rolled sheet subjected to the solution treatment was used as a plate-shaped specimen machine-finished to a thickness of 5.0 mm, while for the comparative example, the cold-rolled sheet of Comparative Example 1 was used. Using 1.0 mm thick plate specimens that had been solution-treated, all were cut out so that the total surface area of the sample was about 7.5 cm ² , and the sample surface was polished using # 500 SiC abrasive paper Then, it was washed with acetone to obtain a test piece. The dissolution test was performed by the immersion test method with reference to JIS G 0591.
The metal species whose elution amount was measured were Fe, Cr, Ni and Mo. The metal elution conditions were 10% H ₂ SO ₄ solution with a liquid temperature of 30 ° C. ± 2 ° C., and the immersion solution amount was 225 ml (of the test piece). a surface area 1 cm ² per 30 ml), the sampling for the elution amount measured, was immersed after the start 0hr, 1hr, 8hr, 24hr, 56hr, and 168 hr (7 days), taken quantity of one dip solution was 10 ml. Quantitative analysis of the elution amount of each metal of Fe, Cr, Ni and Mo was performed by ICP emission analysis or ICP mass spectrometry. The measurement result was converted from the elution amount of each metal (μg / ml) to the elution amount per unit surface area of the test piece (μg / cm ² ). The results are shown in Table 2. In Table 1, PRE = Cr + 3 × Mo + 10 × N (unit of each component is mass%) based on the chemical component composition of the test material as a formula often adopted as the corrosion resistance index (PRE) of stainless steel. The calculated values used are also shown.

(Example, dissolution test results of Comparative Example 1)

From the dissolution test results shown in Table 2, the following matters can be understood.
In the examples within the scope of the present invention, very little elution of Fe and Cr was detected. For example, after elapse of 168 hours (7 days), elution of Fe of 1.83 μg / cm ² , Cr of 0.24 μg / cm ² , and elution of Ni and Mo were not detected at all. On the other hand, in Comparative Example 1 (conventional SUS316L material) outside the scope of the present invention, elution was observed for all of Fe, Cr, Ni and Mo. That is, after elapse of 168 hours (7 days), Fe was 472.0 μg / cm ² , Cr was 124.4 μg / cm ² , Ni was 81.48 μg / cm ² , and Mo was 16.68 μg / cm ² . As a result, about 250 times of elution was observed for Fe and about 500 times of elution was observed for Cr. As described above, it was confirmed that the corrosion resistance was remarkably improved in the examples as compared with the conventional materials.

(2) Power generation test method and test results The power generation test was performed as follows.
About the Example, the said plate-shaped test material of thickness 5.0mm was used, and about the comparative example, the stainless steel plate test material of said thickness 6.0mm (a component composition is the comparative example 2 of Table 1). For each of the examples and comparative examples, machined to 80 × 80 mm, buffed and polished for 15 minutes in hexane, and then the serpentine processed area was 50 × 50 mm, groove depth: 1 mm, groove width: 1 mm, groove interval: 1 mm, machined to prepare a separator, using this to constitute a single cell, under the following power generation conditions,
(A) A cell voltage-time test and (b) a voltage-current test were performed. The power generation conditions are as follows.
Anode gas: pure hydrogen (utilization rate 70%, humidification temperature 70 ° C)
Cathode gas: Air (utilization rate 40%, humidification temperature 70 ° C)
MEA: Commercially available product (PRIMEA5510 manufactured by Japan Gore-Tex)
(50mm x 50mm)
However, PRIMEA is a registered trademark of Japan Gore-Tex Corporation.
Tightening pressure: 150 N / cm ²
Current density: 0.5 A / cm ²

FIG. 4 shows cell voltage-time test results in Examples and Comparative Examples. According to this, although the difference of the cell voltage drop of an Example and a comparative example is not necessarily clear, it seems that the curve of an Example and a comparative example cross | intersects in 700 hour progress vicinity.
Therefore, the voltage-current (Vi) characteristics at the start of power generation and when 1000 hours have elapsed are compared. FIG. 5 and FIG. 6 show the Vi characteristics in Examples and Comparative Examples, respectively. According to FIG. 5, the Vi characteristics of the example hardly deteriorate even after 1000 hours. On the other hand, according to FIG. 6, the Vi characteristic of the comparative example clearly decreases after 1000 hours.
From the above results, it can be seen that the power generation characteristics of the example are clearly superior to those of the comparative example, although the result is a relatively short time of 1000 hours.

It is the schematic explaining the structure of the single cell of a polymer electrolyte fuel cell. It is the schematic explaining the cell stack of a polymer electrolyte fuel cell, and its whole structure. It is a schematic perspective view of a nitrogen addition type consumable electrode when adding Ca by the improved pressurization type ESR process in this invention. FIG. 4 is a horizontal sectional view of FIG. 3. It is a graph which shows the cell voltage-time test result in the separator of an Example and a comparative example. It is a graph which shows the voltage-current test result in the separator of an Example. It is a graph which shows the voltage-current test result in the separator of a comparative example.

Explanation of symbols

1 Fuel Cell Single Cell 2 Solid Polymer Electrolyte Membrane 3 Fuel Electrode Membrane (Anode)
3a Anode catalyst layer 4 Oxidant electrode membrane (cathode)
4a Cathode catalyst layer 5 Membrane electrode assembly (MEA)
6, 7 Separator 6a, 7a Flow path 8, 9 Current collector
10 Fuel gas 11 Oxidizing gas 12 Consumable electrode with nitrogen addition (when Ca is added)
13 Consumable Base Electrode 14 Groove 15 Nitrogen Additive Body 16 Metal Ca Wire 17 Stainless Steel Pipe 18 Sintered Chromium Nitride Powder 19 Cooling Water 20 Restraining Plate 21 Insulating Paper

Claims (3)

A separator sandwiching a solid polymer electrolyte membrane in a fuel cell, the chemical component composition (unit: mass%),
0 <C ≦ 0.08
0 ≦ Si ≦ 0.50
0 ≦ Mn ≦ 0.30
P ≦ 0.020
S ≦ 0.002
O ≦ 0.005
19.0 ≦ Cr ≦ 28.0
Ni ≦ 0.01
1.0 ≦ Mo ≦ 3.0 and 1.00 <N ≦ 2.00
And 0 ≦ Ca <0.0050 and 0.0005 ≦ sol. A separator for a polymer electrolyte fuel cell, characterized in that the base material is stainless steel containing at least one of Al ≦ 0.020, the balance being Fe and inevitable impurities. 2. The polymer electrolyte fuel cell separator according to claim 1, wherein the stainless steel has the following components in a chemical component composition (unit: mass%):
0 <C ≦ 0.03
0 ≦ Si ≦ 0.30
0 ≦ Mn ≦ 0.10
O ≦ 0.003
Ni ≦ 0.005
A separator for a polymer electrolyte fuel cell.   A method for producing stainless steel for use in the separator of the polymer electrolyte fuel cell according to claim 1 or claim 2, wherein the ingot of stainless steel is processed into a slab shape by hot forging. After that, a method for producing stainless steel for a separator of a polymer electrolyte fuel cell, characterized by subjecting the obtained hot-rolled stainless steel plate to hot rolling, subjecting the resulting hot-rolled stainless steel plate to a solution treatment, and pickling the solution.