JP2000294255A - Solid high polymer fuel cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To extremely reduce poisoning of respective electrode carrying catalysts by an eluting metallic ion by constituting a separator of ferrite stainless steel including C, Mn, S, V, Ni, Al, Si, P, N, Cu, Cr and Mo having the specific composition. SOLUTION: Ferrite stainless steel for constituting a separator has the following composition. Respective component elements of C not more than 0.012%, Si of 0.01 to 0.6%, Mn of 0.01 to 0.6%, P not more than 0.026%, S not more than 0.004%, N not more than 0.02%, V of 0.2%, Cu of 0.01 to 0.8%, Ni of 0.2 to 6%, Cr of 10.5 to 35%, Al of 0.001 to 0.2% and Mo of 0 to 6% are included in wt.%. The content of C, N, Cr and Mo falls within a range for satisfying the following two relationships. (C+N<=0.03% and 10.5%<=Cr+3Mo<=43%) are realized, and here, respective atomic symbols show the content (wt.%) of the elements.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer electrolyte fuel cell used as a small distributed power source for a vehicle or a home.

[0002]

2. Description of the Related Art A fuel cell is a cell that generates DC power using hydrogen and oxygen, and is a solid electrolyte fuel cell, a molten carbonate fuel cell, a phosphoric acid fuel cell, and a polymer electrolyte fuel cell. and so on. The name of the fuel cell is derived from the constituent materials of the "electrolyte" part that forms the basis of the cell.

At present, fuel cells that have reached the commercial stage include a phosphoric acid fuel cell and a molten carbonate fuel cell.
Approximate operating temperatures of the fuel cell are 1000 ° C. for a solid oxide fuel cell, 650 ° C. for a molten carbonate fuel cell, 200 ° C. for a phosphoric acid fuel cell, and 80 ° C. for a polymer electrolyte fuel cell.

A solid oxide fuel cell has an operating temperature of 80
Since it is easy to start and stop at low temperatures around ℃ and the energy efficiency can be expected to be about 40%, it can be used as an emergency dispersed power source for small business establishments and telephone offices, a small household dispersed power source using city gas as fuel, and hydrogen gas. It is expected to be put to practical use worldwide as a power source for low-pollution electric vehicles using methanol or gasoline as fuel.

[0005] The above-mentioned various fuel cells are referred to by a common name of "fuel cell", but when considering the constituent materials of the respective cells, it is necessary to consider them completely different. The performance required by the presence or absence of corrosion of the constituent materials due to the electrolyte used, the presence or absence of high-temperature oxidation that begins to become apparent at around 380 ° C, the presence or absence of sublimation and reprecipitation of the electrolyte, the presence of condensation, etc. Because it is completely different. In fact, the materials used are also various, ranging from graphite-based materials to Ni clad materials, high alloys, and stainless steels.

[0006] It is hardly conceivable to apply the materials used in commercially available phosphoric acid fuel cells and molten carbonate fuel cells to the constituent materials of polymer electrolyte fuel cells.

FIG. 1 is a view showing the structure of a polymer electrolyte fuel cell. FIG. 1 (a) is an exploded view of a fuel cell (single cell), and FIG. 1 (b) is a perspective view of the whole fuel cell. It is. As shown in FIG. 1, the fuel cell 1 is an aggregate of single cells. In the single cell, as shown in FIG. 1A, a solid polymer electrolyte membrane 2 has a fuel electrode membrane (anode) 3 laminated on one surface and an oxidant electrode membrane (cathode) 4 laminated on the other surface. It has a structure in which separators 5a and 5b are overlapped on both surfaces.

A typical solid polymer electrolyte membrane 2 includes:
There is a fluorine ion exchange resin membrane having a hydrogen ion (proton) exchange group.

The fuel electrode film 3 and the oxidant electrode film 4 include
A catalyst layer made of a particulate platinum catalyst, graphite powder, and, if necessary, a fluororesin having a hydrogen ion (proton) exchange group is provided so as to come into contact with a fuel gas or an oxidizing gas.

The flow path 6a provided in the separator 5a
From the fuel gas (hydrogen or hydrogen-containing gas) A to supply hydrogen to the fuel electrode film 3. Also, the separator 5
An oxidizing gas B such as air is flown from a flow path 6b provided in b, and oxygen is supplied. The supply of these gases causes the following electrochemical reaction to generate DC power.

Anode side: H ₂ → 2H ⁺ + 2e Cathode side: (1/2) O ₂ + 2H + 2e ⁻ → H ₂ O The functions required of the polymer electrolyte fuel cell separator are:
(1) a function as a “flow path” for uniformly supplying fuel gas in a plane on the fuel electrode side, and (2) water generated on the cathode side,
A function as a "flow path" that efficiently discharges air and oxygen from the fuel cell together with the carrier gas such as air and oxygen outside the system. (3) Between single cells that maintain low electrical resistance and good electrical conductivity as electrodes for a long time And (4) the function as a "partition wall" between the anode chamber of one cell and the cathode chamber of an adjacent cell in an adjacent cell.

Until now, the use of a carbon plate as a separator material has been intensively studied. However, the carbon plate has a problem that it is easily cracked. Further, the machining cost for flattening the surface and the gas flow path are reduced. There is a problem that the machining cost for forming is very high. Each is a fatal issue, and there are situations that can make commercialization of fuel cells themselves difficult.

[0013] Among carbons, a heat-expandable graphite product has been receiving the most attention as a material for a polymer electrolyte fuel cell separator because it is extremely inexpensive. However, in order to reduce the gas permeability and impart the function as the partition wall, the resin impregnation and firing must be performed “a plurality of times”. In addition, there are many issues to be solved in the future, such as machining costs for securing flatness and forming grooves,
At present, it has not been put to practical use.

[0014] In response to the study of the application of such graphite materials, attempts have been made to apply stainless steel to the separator for the purpose of cost reduction.

Japanese Patent Application Laid-Open No. 10-228914 discloses a fuel cell separator made of a metal member and having a gold plating directly applied to a contact surface of a unit cell with an electrode. Stainless steel, aluminum, and Ni-iron alloy are listed as metal members, and SUS304 is used as stainless steel. In the present invention,
It is said that since the separator is plated with gold, the contact resistance between the separator and the electrode is reduced, and the conduction of electrons from the separator to the electrode is improved, so that the output voltage of the fuel cell is increased.

JP-A-8-180883 discloses a solid polymer electrolyte fuel cell in which a passive film formed on the surface uses a separator made of a metal material that is easily formed by the atmosphere. I have. Stainless steel and titanium alloy are mentioned as metal materials. In the present invention, a passivation film is always present on the surface of the metal used for the separator, and the degree of ionization of water generated in the fuel cell is reduced due to the fact that the surface of the metal is hardly chemically attacked. The fuel cell is said to be reduced, and a decrease in the electrochemical reactivity of the fuel cell is suppressed. Further, it is said that the electrical contact resistance value is reduced by removing the passive body film at the portion of the separator that contacts the electrode film or the like and forming a noble metal layer.

However, even if a metal material such as stainless steel provided with a passivation film on the surface disclosed in the above-mentioned publication is used for the separator as it is, the corrosion resistance is not sufficient and the metal is eluted, and the metal eluted. The supported catalyst performance is degraded by ions (hereinafter, referred to as poisoning of the supported catalyst).
In addition, corrosion products such as Cr-OH and Fe-OH generated after elution have a problem that the contact resistance of the separator increases. At present, noble metal plating is applied.

The application of metal materials to separators so far has only been applied, and is far from practical use.

As a separator, which can be applied “pure” without expensive surface treatment and has excellent electric conductivity in a battery environment and stainless steel excellent in corrosion resistance, the production cost of a fuel cell will increase. This is a drastic decrease, and the commercialization of polymer electrolyte fuel cells and the expansion of applications can be expected.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the need for expensive surface treatment, to minimize the poisoning of each electrode-carrying catalyst by metal ions eluted, and to reduce the contact electric contact with electrodes by corrosion products. An object of the present invention is to provide a solid oxide fuel cell provided with a stainless steel separator in which the increase in resistance and the increase in contact resistance due to the strengthening of a passive film are small.

[0021]

The gist of the present invention is as follows.

A plurality of unit cells in which the fuel electrode film and the oxidant electrode film are overlapped with the solid polymer electrolyte membrane in the center, and a laminate in which a separator is interposed between the unit cells,
A solid polymer fuel cell for generating direct current power by supplying a fuel gas and an oxidizing gas, wherein the separator is made of a ferritic stainless steel having the following chemical composition (1) or (2): Polymer fuel cell.

(1) By weight%, C: 0.012% or less, Si: 0.01 to 0.6%, Mn: 0.01 to 0.6%, P: 0.026% or less, S: 0.004% or less, N: 0.02% or less, V: 0.2% or less, Cu: 0.01 to 0.8%, Ni: 0.2 to 6%, Cr: 10.5 to 35% , Al: 0.001 to 0.2%, Mo: 0 to 6%, and the contents of C, N, Cr and Mo are within a range satisfying the following formula: C + N ≦ 0.03% ·········· 10.5% ≦ Cr + 3Mo ≦ 43% ···························································································· ) In weight%, C: 0.012% or less, Si: 0.01 to 0.6%, Mn: 0.01 to 0.6%, P: 0.026% or less, S: 0.004% or less , : 0.02% or less, V: 0.2% or less, Cu: 0.01 to 0.8%, Ni: 0.2 to 6%, Cr: 10.5 to 35%, Al: 0.001 to 0.2%, Mo: 0-6%, Nb: 0.001-0.3%, Ti: 0.00
1 to 0.15% or both, and C,
The contents of N, Cr and Mo satisfy the following formula and
The content of Nb and Ti is within a range satisfying the following expression and / or C + N ≦ 0.03% 10.5% ≦ Cr + 3Mo ≦ 43% 6 ≦ Nb / C ≦ 25 6 ≦ Ti / (C + N) ≦ 25 ········································································································ Separator has the above-mentioned four functions. That is, a) a function as a "flow path" for uniformly supplying the fuel gas in-plane on the fuel electrode side, and b) water generated on the cathode side is efficiently used together with a carrier gas such as air and oxygen reacted from the fuel cell. "Flow path" to be discharged out of the system
C) electrical "connector" between single cells that maintains low electrical resistance and good electrical conductivity as an electrode for a long time
And d) an adjacent cell has a function as a "partition wall" between the anode chamber of one cell and the cathode chamber of the adjacent cell. In some cases, the functions are shared by a plurality of plates. As used herein, the term “separator” refers to a plate having at least one of the above four functions.

The present inventors have developed a polymer electrolyte fuel cell having a separator made of stainless steel,
In an environment where the separator is placed, various tests were performed using a single cell with the aim of reducing as much as possible the metal ions eluted from the stainless steel surface. as a result,
The present invention has been completed based on the following findings.

A) In an environment where the pH of the separator is as low as 1 to 3 (hereinafter simply referred to as the separator environment), the austenitic stainless steel has insufficient corrosion resistance, remarkably elutes metals, and is not suitable for a separator. It is.

B) In a separator environment, ferritic stainless steel exhibits good corrosion resistance, but general ferritic stainless steel elutes a metal to such an extent as to affect battery performance.

C) When the metal elutes, the corrosion product (Fe
(Mainly a hydroxide), which causes an increase in the contact electric resistance and has a remarkable adverse effect on the performance of the supported catalyst, so that the battery performance represented by electromotive force is deteriorated in a short time.
In addition, the cation conductivity of the fluorinated ion exchange resin membrane having hydrogen ion (proton) exchange groups is adversely affected.

D) In order to prevent metal elution, among impurities in ferritic stainless steel, S, P, V,
It is necessary to reduce the Mn content and to strengthen the passive film.

E) Even if the passive film is made strong, if the film thickness is increased, the contact electric resistance is increased, and the battery efficiency is significantly reduced.

F) In order to strengthen the passivation film, the ferritic stainless steel should contain appropriate amounts of Cu and Ni, whereby the passivation of the steel surface is promoted and the passivation holding current density is increased. And is extremely effective in reducing the amount of eluted ions.

G) In particular, the synergistic effect of the reduction of S and the addition of a combination of Cu and Ni is great for preventing metal elution in the separator environment.

H) In order to suppress the elution of metals in the separator environment, the pH at 25 ° C. must be 2.6 and the passive state must be maintained in an aqueous sulfuric acid solution heated to 80 ° C. That is, in the above sulfuric acid solution, 0.2 V
vs. Passive maintenance current density in SCE is 50μA / c
m ² or less.

I) For this purpose, the content of Cr and Mo must be such that (Cr + 3Mo) is in the range of 10.5 to 43%.

J) If Mo is contained, corrosion resistance is ensured, and even if Mo is eluted, the effect on the performance of the catalyst carried on the anode and the cathode is relatively small.

[0035]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The reason why the chemical composition of the ferrite stainless steel separator provided in the polymer electrolyte fuel cell of the present invention is specified will be described in detail below.
In addition,% display of the following components shows weight%.

C, N: C and N in steel are set to 0.012% or less, N to 0.02% or less, and 0.03% or less in C + N value for the purpose of improving room temperature toughness. It is necessary. C and N are intrusion-type elements and cause deterioration of base metal toughness, corrosion resistance of welds, and toughness of high-purity ferritic stainless steel. Strictly limiting C and N is a measure against hot-rolled coil toughness in the manufacturing process of high-purity ferritic stainless steel, and can avoid an increase in manufacturing cost. Room temperature toughness improves as C and N in steel are made extremely low, so the lower the better, the better.

Si: The amount of Si in the steel is 0.01 to 0.6.
%. Si is a deoxidizing element as effective as Al in mass-produced steel. 0.01
If it is less than 0.6%, the deoxidation becomes insufficient, while if it exceeds 0.6%, the moldability decreases.
%. 0.1% to 0.25% is most desirable from the viewpoint of improving productivity, moldability and reducing production cost.

Mn: Mn content in steel is 0.01-0.6%
Must be within the range. Usually, Mn has an effect of fixing S in steel as Mn-based sulfide, and has an effect of improving hot workability. Also, deoxidizing element or N
You may add positively as an i balance adjustment element. To obtain these effects, 0.01% or more is required.
On the other hand, the upper limit is 0.6%. This is because the elution of the metal progresses little by little even in the state where the passive state is maintained, but when the amount exceeds 0.6%, the eluted Mn ions become poisoned to the anode and cathode catalyst layers. This is because the influence is not so small.

P: The amount of P in steel must be 0.026% or less. The P content level of ordinary stainless commercial steel is about 0.026% to 0.035%.
For the separator, P is the most harmful impurity along with S. The lower the better.

S: The amount of S in steel must be 0.004% or less. S is a Mn-based sulfide, a Cr-based sulfide, a Fe-based sulfide, a Ti-based sulfide, a composite non-metal with these composite sulfides and oxides, depending on the coexisting element in the steel and the amount of S in the steel. Most are precipitated as inclusions.
However, in a separator environment, non-metallic inclusions of any composition, although varying in degree, act as a starting point of corrosion and are harmful to maintaining passivation and suppressing corrosion elution.

When the fuel cell is operating, the separator made of ferritic stainless steel and the M
In the gap between EA (Membrane Electrode Assembly)
Due to the battery reaction and / or oxygen concentration difference battery corrosion, the pH in the gap is lowered and micro battery corrosion is likely to occur. However, sulfide-based nonmetallic inclusions are corrosion starting points and acceleration factors at that time. Have a big impact. S content in normal mass-produced steel exceeds 0.005% and 0.008%
Before and after, it is necessary to reduce it to 0.004% or less in order to prevent the above harmful effects. The desirable S content in steel is 0.002% or less, and the most desirable S content level in steel is less than 0.001%, the lower the better.

V: V in steel must be 0.2% or less. In general, V is contained as an impurity in a Cr source, which is an essential melting raw material when smelting stainless steel, and it is unavoidable to mix V to some extent. However, the eluted V
Has a considerable adverse effect on the performance of the catalyst supported on the anode and cathode parts. From the viewpoint of maintaining battery characteristics, the allowable upper limit is 0.2%, and the lower the better, the better.

Cu: Cu must be 0.01 to 0.8%. Ferritic stainless steels can be used in a pH environment above the critical pH where the passive film becomes unstable.
It shows superior corrosion resistance compared to austenitic stainless steel containing a large amount of i, and has a feature that the dissolution rate in the passive state is low. This feature is further improved by adding Cu to the ferritic stainless steel.

When a proper amount of Cu is added to reduce the metal elution from a material in a passive state including a separator environment for a polymer electrolyte fuel cell, passivation is promoted, and a passive state current density is increased. Is extremely effective in lowering The remarkable improvement in the degree of passivation is extremely effective for reducing the amount of eluted metal ions, and is therefore extremely effective for remarkably improving the degree of catalyst poisoning by the eluted metal ions. is there. In order to obtain these effects, it is necessary to contain 0.01% or more, and when it exceeds 0.8%, the effects are almost saturated, which causes a reduction in manufacturability and an increase in manufacturing cost. Therefore, Cu
The content was 0.01 to 0.8%. 0.15-0.6
5% is most effective.

Ni: Ni content needs to be in the range of 0.2 to 6%. Ni, like Cu, has the effect of stabilizing the passive film of ferritic stainless steel and reducing the metal elution rate in the passive state maintained in a pH environment above the critical pH where the passive film becomes unstable. Have. The inclusion of Ni reduces the metal elution in the passive environment holding state in the separator environment, and significantly improves the degree of catalyst poisoning by the eluted metal ions. To obtain this effect, 0.2% or more is required.

This effect of Ni becomes more remarkable especially when it is contained in a composite with Cu and the amount of S is reduced. However, if it exceeds 6%, a two-phase structure of ferrite-austenite or a martensite structure is obtained, and the formability is deteriorated. In a two-phase structure, the directionality of the formability is increased, and in the martensite system, the strength is increased, which is unsuitable for applications requiring forming of a steel sheet such as a separator.

Cr, Mo: Cr and Mo are both basic alloying elements for ensuring corrosion resistance. The higher the content, the higher the corrosion resistance, but the higher the Cr content, the lower the room temperature toughness tends to be. If the Cr content exceeds 35%, mass production becomes difficult. If it is less than 10.5%, it becomes difficult to secure the corrosion resistance required for a separator even if other elements are changed.

Mo is an element to be contained if necessary.
The effect of improving corrosion resistance is small with a small amount. If the content exceeds 6%, it is difficult to avoid precipitation of an intermetallic compound such as a sigma phase, and production becomes difficult due to the problem of embrittlement of steel. Therefore, the upper limit is set to 6%. By positively containing Mo, corrosion resistance is ensured. Even if Mo elutes, the effect on the performance of the catalyst supported on the anode and the cathode is relatively small.

(Cr% + 3 Mo%): The stainless steel for the separator is in a passivated state in an environment of 70 ° C. to 100 ° C. at most, which is the operating temperature of the polymer electrolyte fuel cell, and it is continuous. In addition, it is necessary that the contact electric resistance is low. It is necessary to suppress the increase in the thickness of the passive film and the formation of corrosion products within a practical range. As a necessary condition for this, it is determined that it is appropriate as a simulated environment inside the battery in an actual operating state. "If the pH at 25 ° C is 2.
6 at 80 ° C. in an aqueous solution of sulfuric acid ”. In this environment, the passive state maintaining current density at 0.2 V vs. SCE needs to be 50 μA / cm ² or less. In order to satisfy this condition, at least C
The content of r and Mo is the corrosion index (Cr% + 3
Mo%) must be in the range of 10.5 to 43%.

Al: Al is effective for deoxidation, and 0.001% or more is required to obtain the effect. However, if it exceeds 0.2%, further improved hardening will not be observed, and the production cost will increase too much.

Nb, Ti: The bonding force between C and N in steel is Cr.
One or two of Nb and Ti, which are stronger alloying elements, are contained as necessary. Nb is 0.001 to
0.3%, Nb (%) / C (%) is in the range of 6 to 25, Ti is 0.001 to 0.15%, and Ti is
(%) / C + N (%) is in the range of 6 to 25.

Nb and Ti are extremely effective in improving low-temperature toughness. It has a great effect on improving the formability of steel sheets. However, Nb eluted with the corrosion accumulates as a corrosion product on the corroded surface and has a problem of increasing the contact electric resistance. In addition, Ti eluted due to corrosion has the harm of lowering the performance of the catalyst carried on the anode and cathode of the polymer electrolyte fuel cell. Therefore, when it is contained, it is necessary to make the necessary minimum amount, and within the above range, the above effects can be obtained and the above-mentioned adverse effects can be avoided. Also,
By simultaneously adding Nb and Ti, the workability of the cold-rolled steel sheet material is improved.

Rare earth element (REM): The rare earth element renders S harmless because it has an extremely strong bonding force with S in the molten steel stage. If necessary, it may be contained in the form of misch metal. A sufficient effect can be obtained when the content is as small as 0.1% or less.

If necessary, an element other than the above elements may be contained. For example, in order to improve the hot workability, it is preferable to contain a small amount of Ca, Mg or B of 0.1 or less.

[0055]

EXAMPLES Ferritic stainless steels having 26 kinds of chemical compositions shown in Table 1 were melted in a high-frequency induction heating type 150 kg vacuum melting furnace. As the melting raw material, a commercially available raw material having a small amount of impurities was carefully selected and used, and the amount of impurities in the steel was adjusted.

[0056]

[Table 1]

The ingot having a round cross section was heated to 1230 ° C. for 3 hours in the atmosphere, and then hot forged with a press-type forging machine, and each ingot was formed into a test slab having the following two dimensions. Finished.

Thickness 30 mm, width 100 mm, length 12
A slab having a thickness of 0 mm, a thickness of 70 mm, a width of 380 mm, and a length of 550 mm is hot-rolled into a hot-rolled steel sheet having a thickness of 6 mm, and then gradually cooled under heat insulating material wrapping conditions simulating the temperature history immediately after the end of hot rolling in mass production. did. A Charpy impact test was conducted to examine the toughness of the hot rolled coil at room temperature. The test piece was JIS-4 half size. The slab is machined by cutting the slab surface
The oxide scale on the surface was removed, and the slab was finished to a thickness of 62 mm. This slab is heated to 1200 ° C in the atmosphere,
After finishing to a thickness of 4 mm by hot rolling, as in the case of the above, the material was gradually cooled under heat insulating material wrapping conditions simulating the temperature history immediately after the end of hot rolling in mass production.

This hot-rolled steel sheet was subjected to a solution treatment for 4 minutes at the following temperature according to the chemical composition, and was forcibly air-cooled. Hot-rolled steel sheets of No. 1 to 4, 15 to 20 in Table 1 having a chemical composition of 930 ° C. Hot-rolled steel sheets of No. 5 to 8, 12, 13, 21, and 22 in Table 1... 1000 C. Hot rolled steel sheets of Nos. 9 to 11 and 23 to 26 in Table 1... 1080 C. Each temperature was set to a temperature at which recrystallization proceeds and an intermetallic compound forms a solid solution. Furnace time was approximately 20 minutes.

Next, the hot-rolled steel sheet subjected to the solution treatment was cold-rolled using a multi-stage Sendzimer-type roll rolling mill while sandwiching intermediate annealing on the way, and finished to a thickness of 0.3 mm. The final finish annealing was performed in a bright annealing furnace in a hydrogen atmosphere having a dew point of −50 ° C. or less, and the temperature was the same as the annealing temperature of the hot-rolled material. The holding time was 1 minute, and the oven time was about 3 minutes.

From this cold-rolled annealed material, a test piece for evaluating a passive film in a simulated separator having the following dimensions and a separator for loading into an actual polymer electrolyte fuel cell were formed by press molding. Made.

For No. 27 of Comparative Example, a test piece for a simulated environment and a separator were prepared, and then gold plating was applied to a thickness of 5 μm on one side.

Test specimen for simulated environment: thickness 0.3 mm, width 10 mm, length 10 mm Separator: thickness 0.3 mm, length 80 mm, width 80 mm Gas flow path: height 0.8 mm, gap between peaks 1.2mm
(Corrugating) These surfaces are shot
Mechanically shot-polished using iC abrasives, 5%
Ultrasonic cleaning is performed for 15 minutes in HNO ₃ + 3% HF at 40 ° C. Further, immediately before the test, alkali spray degreasing using a 6% aqueous sodium hydroxide solution is performed. Distilled water immersion cleaning was performed three times, and distilled water spray cleaning was further performed for 4 minutes to dry with a cool air dryer, and then subjected to each test.

As a test in a simulated environment, an aqueous sulfuric acid solution having a pH of 2.6 at 25 ° C. prepared using sulfuric acid as a special grade reagent was heated to 80 ° C., and the test piece was immersed in the solution for 6 hours. . The presence or absence of passivation is evaluated from the loss of corrosion, the presence or absence of hydrogen bubbles from the surface of the material, and the color change of the test solution.
The passive holding current density at 0.2 V vs SCE was measured.

Table 2 shows the results of the Charpy impact test and the test results in the simulated separator environment.

[0066]

[Table 2]

As is apparent from Table 2, in the present invention,
It is in a passivated state in an aqueous sulfuric acid solution having a pH of 2.6 at 25 ° C. at a temperature raised to 80 ° C., and the “passive holding current density” indicating the degree of elution is also 30 μA / cm ² or less.

When stainless steel is applied as a separator for a polymer electrolyte fuel cell, it is needless to say that it is desirable to keep the passive state holding current density as low as possible. It is important to take a stable low value,
Less than 10 μA / cm ² is most desirable, then 10-20
μA / cm ² is desirable.

The passive state holding current density of the comparative example is 50 to 70.
μA / cm ² , which can be said to be suppressed, but indicates that relatively large elution has occurred from the separator.

The present inventors determined that the passive state holding current> 50 as a criterion for judging the applicability as a fuel cell separator material in relation to the performance characteristics of an actual single cell battery.
It was determined that the performance was insufficient at μm / cm ² . For materials with a passive state current density of 50 μm / cm ² or less, even a real single-cell evaluation test has not been able to confirm the time-dependent deterioration of a problematic degree, which is extremely suitable as a rapid simulation environment evaluation condition. Is determined to be. Also in the present results, in the case of the invention example, it is at the same level as the gold plating material (test steel 27) which is one of the most desirable metal materials in the polymer electrolyte fuel cell environment. It was determined that it could be secured.

Next, as an evaluation of the characteristics in a state where the separator is loaded inside the actual solid polymer type single cell battery,
One hour after the flow of the fuel gas into the battery, the voltage of the single cell battery was measured and compared with the initial voltage to determine the rate of voltage decrease. The rate of decrease was determined by 1− (voltage V after one hour has elapsed / initial voltage v).

The polymer electrolyte fuel cell used in the evaluation was a modified battery cell “FC50 (trade name)” manufactured by Electrochem, USA.

The gas for fuel on the anode side is 99.9.
999% hydrogen gas was used, and air was used as the cathode electrode side gas. The entire body of the battery was kept at 78 ± 2 ° C., and the humidity control inside the battery was adjusted on the entry side based on the measurement of the exhaust gas moisture concentration on the cell exit side. Set humidity is 78 ±
2 ° C. The pressure inside the battery is 1 atm. Introducing gas pressure of hydrogen gas and air into the battery is 0.04-0.20b
Adjusted with ar. The cell performance was evaluated at a single cell voltage of 500.
mA / cm ² −0.62 V The measurement was continuously performed from the state where it was confirmed that the voltage became 0.62 V.

As a single cell performance measuring system, a modified fuel cell measuring system based on the 890 series manufactured by Scribner, USA was used. It is expected that the characteristics will change depending on the battery operating state, but this is a comparative evaluation under the same conditions.

Table 2 shows the results.

As is clear from Table 2, the voltage drop rates of all the examples of the present invention were 0.05 or less, which was equivalent to that of the No. 27 expensive and highly corrosion-resistant gold-plated separator. On the other hand, in Comparative Examples in which the chemical compositions deviated from those defined in the present invention, the voltage drop rate was extremely large, 0.2 to 0.8.

Some of the test pieces were evaluated by performing a long-term test, and a correlation result similar to the short-term test result shown in Table 2 was obtained.

The toughness of stainless steel at room temperature is generally inferior to ferritic stainless steel as compared to austenitic stainless steel. However, as is clear from the Charpy test results in Table 2, the series of examples of the present invention having lower C and N contents are much superior to the comparative examples having higher C and N contents in steel. It has high toughness. That is,
It can be said that the hot-rolled coil room-temperature toughness, which is a problem when producing high-purity ferritic stainless steel, is good. In general, the room temperature toughness is apparently improved as the sheet thickness is reduced, and therefore there is no practical problem at the level of the steel of the present invention.

[0079]

The polymer electrolyte fuel cell of the present invention can be manufactured at a low cost because the separator is made of ferritic stainless steel and does not require expensive gold plating.

[Brief description of the drawings]

FIG. 1 is a diagram showing a structure of a polymer electrolyte fuel cell.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Fuel cell 2 Solid molecular electrolyte membrane 3 Fuel electrode membrane 4 Oxidizer electrode membrane 5a, 5b Separator

Continuation of the front page (72) Inventor: Norifumi Doi 4-5-33 Kitahama, Chuo-ku, Osaka-shi, Osaka Sumitomo Metal Industries, Ltd. F-term (reference) 5H026 AA06 CC03 EE08 HH05

Claims (2)

[Claims] 1. A laminate in which a plurality of unit cells in which a fuel electrode membrane and an oxidant electrode membrane are overlapped with a solid polymer electrolyte membrane in the center, and a separator is interposed between the unit cells,
A polymer electrolyte fuel cell for supplying a fuel gas and an oxidant gas to generate DC power, wherein the separator is made of a ferritic stainless steel having the following chemical composition. By weight%, C: 0.012% or less, Si: 0.01 to 0.6%, Mn: 0.01 to 0.6%, P: 0.026% or less, S: 0.004% or less, N: 0.02% or less, V: 0.2% or less, Cu: 0.01 to 0.8%, Ni: 0.2 to 6%, Cr: 10.5 to 35%, Al: 0.001 0.2%, Mo: 0-6%, and the contents of C, N, Cr and Mo are within a range satisfying the following formula: C + N ≦ 0.03% ········ 10.5% ≦ Cr + 3 × Mo ≦ 43% ·················································································. 2. A laminate in which a plurality of unit cells in which a fuel electrode membrane and an oxidant electrode membrane are overlapped with the solid polymer electrolyte membrane in the center, and a separator is interposed between the unit cells,
A polymer electrolyte fuel cell for supplying a fuel gas and an oxidant gas to generate DC power, wherein the separator is made of a ferritic stainless steel having the following chemical composition. C: 0.012% or less, Si: 0.01 to 0.6%, Mn: 0.01 to 0.6%, P: 0.026% or less, S: 0.004% or less, N: 0. 02% or less, V: 0.2% or less, Cu: 0.01 to 0.8%, Ni: 0.2 to 6%, Cr: 10.5 to 35%, Al: 0.001 to 0.2 %, Mo: 0 to 6%, Nb: 0.001 to 0.3%, Ti: 0.00
1 to 0.15% or both, and C,
The contents of N, Cr and Mo satisfy the following formula and
The content of Nb and Ti is within a range satisfying the following expression and / or C + N ≦ 0.03% 10.5% ≦ Cr + 3Mo ≦ 43% 6 ≦ Nb / C ≦ 25 6 ≦ Ti / (C + N) ≦ 25 .. Here, the element symbol indicates the content (% by weight) of each element