JP2017208336A - Solid polymer type fuel cell separator part and method for manufacturing solid polymer type fuel cell separator part - Google Patents

Solid polymer type fuel cell separator part and method for manufacturing solid polymer type fuel cell separator part Download PDF

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JP2017208336A
JP2017208336A JP2017095948A JP2017095948A JP2017208336A JP 2017208336 A JP2017208336 A JP 2017208336A JP 2017095948 A JP2017095948 A JP 2017095948A JP 2017095948 A JP2017095948 A JP 2017095948A JP 2017208336 A JP2017208336 A JP 2017208336A
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stainless steel
fuel cell
separator
solid polymer
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JP6856871B2 (en
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昌信 熊谷
Masanobu Kumagai
昌信 熊谷
一郎 吉野
Ichiro Yoshino
一郎 吉野
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Nachi Fujikoshi Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

PROBLEM TO BE SOLVED: To provide: a solid polymer type fuel cell separator part having desired electrical conductivity and corrosion resistance which a separator for fuel cell use is required to have; and a method for manufacturing the solid polymer type fuel cell separator part.SOLUTION: A solid polymer type fuel cell separator part is made of stainless steel. In the stainless steel, crystal grains of 3.0 μm or smaller in diameter account for 60% or more of all of crystal grains. If the stainless steel is austenite stainless steel, an oxygen content in the stainless steel is 30 ppm or less by weight. The solid polymer type fuel cell separator part may be arranged to further comprise a styrene-butadiene rubber attached to the surface thereof, provided that the styrene-butadiene rubber includes titanium nitride particles.SELECTED DRAWING: Figure 1

Description

本発明は、主に車輌、船舶、航空機などの乗物に搭載され、または企業や一般家庭で使用されている燃料電池、特に固体高分子形燃料電池に用いるセパレータ素材、当該素材を用いた固体高分子形燃料電池用セパレータ部品および固体高分子形燃料電池用セパレータの部品の製造方法に関する。   The present invention mainly relates to a fuel cell that is mounted on a vehicle such as a vehicle, a ship, or an aircraft, or is used in a company or a general household, particularly a separator material used for a polymer electrolyte fuel cell, and a solid height using the material. The present invention relates to a method of manufacturing a separator part for a molecular fuel cell and a separator part for a polymer electrolyte fuel cell.

近年、自動車やバスの電源として搭載されている燃料電池や一般家庭向けの電源として提供されている燃料電池は、その多くが固体高分子形燃料電池（ＰＥＦＣまたはＰＥＭＦＣ）である。固体高分子形燃料電池は、りん酸形燃料電池など他の燃料電池に比べて小形かつ軽量化が可能であり、起動時の操作が比較的に容易であることから各産業分野でその普及が進みつつある。そのため固体高分子形燃料電池を構成するセパレータとしては、良好な電気伝導性に加えて、酸における耐食性や加工時における成形性などの諸特性が求められている。   In recent years, many of the fuel cells mounted as power sources for automobiles and buses and the fuel cells provided as power sources for general households are polymer electrolyte fuel cells (PEFC or PEMFC). Solid polymer fuel cells are smaller and lighter than other fuel cells, such as phosphoric acid fuel cells, and are relatively easy to operate at startup. Progressing. Therefore, as a separator constituting the polymer electrolyte fuel cell, various properties such as corrosion resistance in acid and moldability during processing are required in addition to good electrical conductivity.

例えば、特許文献１ではステンレス鋼製の燃料電池用セパレータとして平均結晶粒径が１〜４０μｍの範囲のオーステナイト系ステンレス鋼板が開示されている。オーステナイト系ステンレス鋼板の平均結晶粒径を一定範囲に規定することで、適度な寸法精度と成形性が確保できることが説明されている。   For example, Patent Document 1 discloses an austenitic stainless steel sheet having an average crystal grain size in the range of 1 to 40 μm as a stainless steel fuel cell separator. It is described that an appropriate dimensional accuracy and formability can be ensured by defining the average crystal grain size of the austenitic stainless steel sheet within a certain range.

また、特許文献２にも特許文献１と同様に燃料電池用セパレータ素材としてオーステナイト系ステンレス鋼材の化学成分が開示されている。特に、鋼材中の酸素（Ｏ）濃度については酸化物の生成を抑制、中でも鋼材中の硫黄（Ｓ）と結合することを阻止する観点から比較的に低濃度であることで求められている。これにより、高温雰囲気中における燃料電池用セパレータ素材の耐酸化特性と電気伝導性を実現できることが説明されている。 Similarly to Patent Document 1, Patent Document 2 discloses a chemical component of an austenitic stainless steel material as a fuel cell separator material. In particular, the oxygen (O) concentration in the steel material is required to be a relatively low concentration from the viewpoint of suppressing the formation of oxides and, in particular, preventing bonding with sulfur (S) in the steel material. Thus, it is explained that the oxidation resistance and electrical conductivity of the fuel cell separator material in a high temperature atmosphere can be realized.

特開２００４−３３９５６９号公報Japanese Patent Application Laid-Open No. 2004-339569 特開平１１−２９３９４１号公報Japanese Patent Laid-Open No. 11-293941

しかし、特許文献１に開示されているＰＥＦＣ（固体高分子形燃料電池）用ステンレス鋼製セパレータでは、模擬ＰＥＦＣ環境中（低ｐＨやフッ化物イオンの雰囲気)におけるステンレス鋼の耐食性についてのみ開示されており、通常のステンレス鋼の腐食の起点となる鋼中の介在物（酸化物や硫化物）や鋼中の酸素濃度の影響や実際のＰＥＦＣの環境下でのステンレス鋼製セパレータの耐食性については何ら開示されていない。 However, the stainless steel separator for PEFC (solid polymer fuel cell) disclosed in Patent Document 1 discloses only the corrosion resistance of stainless steel in a simulated PEFC environment (low pH and fluoride ion atmosphere). What is the influence of the inclusions (oxides and sulfides) in the steel, the starting point of corrosion of normal stainless steel, the oxygen concentration in the steel, and the corrosion resistance of the stainless steel separator in the actual PEFC environment? Not disclosed.

また、特許文献２に開示されているＰＥＦＣ（固体高分子形燃料電池）用ステンレス鋼製のセパレータでは、腐食の起点となる鋼中の酸化物や硫化物の影響について、８７３Ｋ 以上の高温酸化雰囲気におけるステンレス鋼の耐食性に限定しており、ＰＥＦＣの作動温度である３５３Ｋ付近でのステンレス鋼の耐食性やステンレス鋼を薄肉化した際の強度や加工性については何ら開示されていない。 In addition, in the stainless steel separator for PEFC (Polymer Polymer Fuel Cell) disclosed in Patent Document 2, a high-temperature oxidizing atmosphere of 873 K or higher with respect to the influence of oxides and sulfides in the steel that is the starting point of corrosion. The corrosion resistance of stainless steel at 353 K, which is the operating temperature of PEFC, and the strength and workability when the stainless steel is thinned are not disclosed.

そこで、本発明においては燃料電池用途のセパレータとして求められる所望の電気伝導性および耐食性を兼ね備えた燃料電池用セパレータ部品を提供することを課題とする。   Therefore, an object of the present invention is to provide a fuel cell separator component that has both desired electrical conductivity and corrosion resistance required as a separator for fuel cell applications.

前述した課題を解決するために、本発明者はステンレス鋼製の固体高分子形燃料電池用セパレータ部品であって、このステンレス鋼の結晶粒径について３．０μｍ以下の結晶粒径が全体に対して占める割合を６０％以上とする。また、ステンレス鋼がオーステナイト系ステンレス鋼である場合には、当該ステンレス鋼に含有される酸素量を質量％で３０ｐｐｍ以下とする固体高分子形燃料電池用セパレータ部品とする。 In order to solve the above-described problems, the present inventor is a separator for a polymer electrolyte fuel cell made of stainless steel, and the crystal grain size of the stainless steel is 3.0 μm or less relative to the whole. The proportion of the total is 60% or more. Further, when the stainless steel is an austenitic stainless steel, a separator for a polymer electrolyte fuel cell in which the amount of oxygen contained in the stainless steel is 30 ppm or less by mass% is used.

また、前述の固体高分子形燃料電池用セパレータ部品の表面に窒化チタン粒子（以下、「ＴｉＮ」という）を含有するスチレンブタジエンゴム（以下、「ＳＢＲ」という）を付着させる固体高分子形燃料電池用セパレータとすることもできる。 Further, a solid polymer fuel cell in which styrene butadiene rubber (hereinafter referred to as “SBR”) containing titanium nitride particles (hereinafter referred to as “TiN”) is attached to the surface of the separator part for a solid polymer fuel cell described above. It can also be used as a separator.

固体高分子形燃料電池用セパレータ部品の製造方法としては、ステンレス鋼の表面を常圧の雰囲気下で８０℃以上２２０℃以下の温度範囲で加熱した状態でＴｉＮ粒子を含むＳＢＲを密着させることができる。また、ステンレス鋼の表面を８０℃以上１００℃以下の温度範囲で加熱した後、１５０℃以上２２０℃以下の温度範囲まで昇温することで前記ステンレス鋼の表面を段階的に加熱しても構わない。 As a method for producing a separator for a polymer electrolyte fuel cell, SBR containing TiN particles is adhered in a state where the surface of stainless steel is heated in a temperature range of 80 ° C. or higher and 220 ° C. or lower in an atmosphere of normal pressure. it can. Further, after the surface of the stainless steel is heated in a temperature range of 80 ° C. or higher and 100 ° C. or lower, the surface of the stainless steel may be heated stepwise by raising the temperature to a temperature range of 150 ° C. or higher and 220 ° C. or lower. Absent.

本発明に係る固体高分子形燃料電池用セパレータ部品とすることで、燃料電池用途のセパレータとして求められる所望の電気伝導性および耐食性の両立を図ることができる。また、本発明の固体高分子形燃料電池用セパレータ部品の製造方法は常圧雰囲気の中で、かつ２００℃前後の加熱温度で素材（ステンレス鋼）にＴｉＮ粒子を含むＳＢＲを付着するので、比較的に低コストでセパレータ部品を製造できるという効果を奏する。 By using the separator part for a polymer electrolyte fuel cell according to the present invention, it is possible to achieve both desired electrical conductivity and corrosion resistance required as a separator for a fuel cell. In addition, the method for producing a separator part for a polymer electrolyte fuel cell according to the present invention attaches SBR containing TiN particles to a material (stainless steel) in a normal pressure atmosphere and at a heating temperature of around 200 ° C. In particular, it is possible to produce separator parts at low cost.

実施例１における本発明材１、２および比較材１〜３をそれぞれ別個に組み込んだ各セルにおける５００時間までの発電試験結果である。It is a power generation test result up to 500 hours in each cell in which the present invention materials 1 and 2 and comparative materials 1 to 3 in Example 1 are separately incorporated. ステンレス鋼の表面にＴｉＮ粒子を含むＳＢＲを付着させた状態を示すＳＥＭ写真である。It is a SEM photograph which shows the state which adhered SBR containing TiN particle | grains to the surface of stainless steel. 実施例２における本発明材１〜４および比較材としての樹脂含浸黒鉛材（比較材４）をそれぞれ別個に組み込んだ各セルにおける５００時間までの発電試験結果である。It is an electric power generation test result to 500 hours in each cell which each incorporated the present invention materials 1-4 in Example 2, and the resin impregnation graphite material (comparative material 4) as a comparison material separately.

本発明の実施の形態の一例について説明する。本発明の固体高分子形燃料電池用セパレータ部品は、ステンレス鋼製とし、鋼種としては例えばオーステナイト系ステンレス鋼やフェライト系ステンレス鋼などが適用できる。 An example of an embodiment of the present invention will be described. The separator part for a polymer electrolyte fuel cell of the present invention is made of stainless steel, and examples of the steel type include austenitic stainless steel and ferritic stainless steel.

また、ステンレス鋼の結晶粒径については、３．０μｍ以下の結晶粒径が全体に対して占める割合を６０％以上とする。ステンレス鋼の結晶粒径の割合を規定した理由は、３．０μｍ以下の結晶粒径が全体に対して占める割合が６０％未満になると、素材たるステンレス鋼をセパレータに加工する特性は向上する（加工しやすくなる）が、セパレータ部品の素材としての材料強度が低下する、もしくは加工工程においてスプリングバックを考慮した金型設計が必要になるためである。 Moreover, about the crystal grain size of stainless steel, the ratio for which the crystal grain size of 3.0 micrometers or less occupies with respect to the whole shall be 60% or more. The reason for specifying the ratio of the crystal grain size of stainless steel is that when the ratio of the crystal grain size of 3.0 μm or less to the whole is less than 60%, the characteristics of processing the stainless steel as a material into a separator are improved ( This is because the strength of the material as the material of the separator component is reduced, or a mold design that takes the spring back into consideration in the processing process is required.

さらに、ステンレス鋼の鋼種がオーステナイト系ステンレス鋼の場合には、当該ステンレス鋼に含有される酸素（Ｏ）量は質量％で３０ｐｐｍ以下とする。オーステナイト系ステンレス鋼に含有される酸素量の上限を３０ｐｐｍに規定した理由は、オーステナイト系ステンレス鋼の酸素量が３０ｐｐｍを超えるとオーステナイト系ステンレス鋼中の酸化物系介在物が増加することでセパレータ部品としての耐食性が低下し、ひいてはセパレータとしての発電効率の低下につながるためである。 Furthermore, when the steel type of the stainless steel is austenitic stainless steel, the amount of oxygen (O) contained in the stainless steel is 30 ppm or less by mass%. The reason why the upper limit of the amount of oxygen contained in the austenitic stainless steel is defined as 30 ppm is that when the oxygen content of the austenitic stainless steel exceeds 30 ppm, the oxide inclusions in the austenitic stainless steel increase, so that separator parts This is because the corrosion resistance of the separator is lowered, and as a result, the power generation efficiency of the separator is lowered.

セパレータ部品の素材（原材料）であるステンレス鋼の表面を改質する方法としては、金メッキ等の貴金属メッキ法やＣＶＤ法やＰＶＤ法によるカーボンや窒化物の被覆、熱窒化法によるクロム窒化物を析出させる方法がある。しかし、表面を改質する際に用いる装置や工程が複雑であることから、本発明では簡便な泳動電着法によりステンレス鋼の表面にＴｉＮ粒子を具備（含有）したＳＢＲを付着させることとした。 As a method of modifying the surface of stainless steel, which is the material (raw material) of separator parts, precious metal plating methods such as gold plating, carbon and nitride coating by CVD method and PVD method, and chromium nitride by thermal nitriding method are deposited. There is a way to make it. However, since the apparatus and process used for modifying the surface are complicated, in the present invention, the SBR containing (containing) TiN particles is attached to the surface of stainless steel by a simple electrophoretic electrodeposition method. .

これにより、電極基板となるガス拡散層（以下、「ＧＤＬ」という）との接触抵抗の低減を図ることができる。ここで泳動電着法とは、導電性粒子を分散させた分散浴中に２枚の電極を浸漬した状態で、これら２枚の電極間に電圧を印加することにより一方の電極上に導電性粒子を吸着、堆積させる方法をいうものとする。 Thereby, the contact resistance with the gas diffusion layer (hereinafter referred to as “GDL”) serving as the electrode substrate can be reduced. Here, the electrophoretic electrodeposition method is a method in which two electrodes are immersed in a dispersion bath in which conductive particles are dispersed, and a voltage is applied between the two electrodes to cause the conductivity on one electrode. A method of adsorbing and depositing particles shall be said.

上述の泳動電着法に使用する分散浴には、例えば分散媒として２−プロパノール、導電性粒子としては平均粒径が５０ｎｍのＴｉＮ粒子、ゴム系のバインダーとしてはＳＢＲをそれぞれ選定することができる。当該分散媒中にはＴｉＮ粒子を０．０５０ｗｔ％、ＳＢＲを０．０７４ｗｔ％の割合で加えた後、超音波振動によりＴｉＮ粒子およびＳＢＲを分散媒中に充分に分散させたものを分散浴とすることができる。 For the dispersion bath used in the electrophoretic electrodeposition method, for example, 2-propanol can be selected as a dispersion medium, TiN particles having an average particle diameter of 50 nm can be selected as conductive particles, and SBR can be selected as a rubber-based binder. . In the dispersion medium, 0.05% by weight of TiN particles and 0.074% by weight of SBR were added, and then the dispersion medium was sufficiently dispersed with TiN particles and SBR by ultrasonic vibration. can do.

本発明材（２水準）および比較材（３水準）をそれぞれ別個のセルに組み込んでセパレータとしての発電試験を行ったので、その試験結果について図面を用いて説明する。本試験に用いた供試材は、まず本発明材としてステンレス鋼に含有される酸素量が重量％で３０ｐｐｍ以下のＳＵＳ３１６Ｌ鋼に対して結晶粒を微細化させたものを用いた（本発明材１〜２の酸素量はすべて２２ｐｐｍ）。本発明材１は表２に示すように結晶粒を微細化させた結果、平均結晶粒径が１．５μｍ、全結晶粒に対して結晶粒径が３．０μｍ以下である結晶粒の占める割合が９６％である供試材である。本発明材２は平均結晶粒径が２．９μｍ、全結晶粒に対して結晶粒径が３．０μｍ以下である結晶粒の占める割合が６３％である供試材である。 Since the inventive material (2 levels) and the comparative material (3 levels) were incorporated in separate cells and a power generation test as a separator was conducted, the test results will be described with reference to the drawings. The test material used in this test was a material obtained by refining crystal grains with respect to SUS316L steel having an oxygen content of 30 ppm or less by weight% as stainless steel according to the present invention. The oxygen amount of 1-2 is all 22 ppm). As a result of refining crystal grains as shown in Table 2, the present invention material 1 has an average crystal grain size of 1.5 μm and a ratio of crystal grains having a crystal grain size of 3.0 μm or less with respect to all crystal grains Is 96%. Invention material 2 is a test material having an average crystal grain size of 2.9 μm, and the proportion of crystal grains having a crystal grain size of 3.0 μm or less with respect to all crystal grains is 63%.

これに対して、結晶粒微細化させていない供試材（以下、「比較材１」という）、ステンレス鋼に含有される酸素量が重量％で３０ｐｐｍ以上のＳＵＳ３１６Ｌ鋼に対して結晶粒を微細化させていない供試材（以下、「比較材２」という）および結晶粒を微細化させた供試材（以下、「比較材３」という）を比較材１〜３とした。本試験に用いた供試材の化学組成（単位：重量％）を表１に、供試材の平均結晶粒径などを表２に、供試材の仕様および試験条件を表３にそれぞれ示す。 On the other hand, the test grains (hereinafter referred to as “Comparative Materials 1”) that have not been refined with crystal grains, and the SUS316L steel with an oxygen content of 30 ppm or more by weight% are finer. The test materials (hereinafter referred to as “Comparative Materials 2”) and the test materials (hereinafter referred to as “Comparative Materials 3”) in which the crystal grains were refined were designated as Comparative Materials 1 to 3. Table 1 shows the chemical composition (unit:% by weight) of the test material used in this test, Table 2 shows the average crystal grain size of the test material, and Table 3 shows the specifications and test conditions of the test material. .

Figure 2017208336
Figure 2017208336

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Figure 2017208336

なお、供試材の厚さ（板厚）は本発明材１、２および比較材３が０．０７ｍｍ、比較材１および２は０．１０ｍｍとした。   The thickness of the test material (plate thickness) was 0.07 mm for the inventive materials 1 and 2 and the comparative material 3, and 0.10 mm for the comparative materials 1 and 2.

本発明材１、２および比較材１〜３のいずれについてのセパレータ部品の溝深さは、流路形成材と流路底板の溝深さが０．５ｍｍとなるように流路底板の溝深さを設定し、当該流路底板に機械加工によりサーペンタイン流路を成型した。また、本発電試験において流路形成材と流路底板が接する面には流路形成材側に接触抵抗を低減する金メッキ処理を施した。   The groove depth of the separator part for any of the inventive materials 1 and 2 and the comparative materials 1 to 3 is such that the groove depth of the flow path forming material and the flow path bottom plate is 0.5 mm. The serpentine channel was formed by machining on the channel bottom plate. In this power generation test, the surface where the flow path forming material and the flow path bottom plate contact each other was subjected to a gold plating process for reducing contact resistance on the flow path forming material side.

本発明材１、２および比較材１〜３をそれぞれ別個に組み込んだ各セルにおける５００時間までの発電試験結果を図１に示す。本試験中における発電試験中のセル電圧の経時変化を図１に示すグラフより直線近似して、本発明材１、２および比較材１〜３の発電開始時のセル電圧と平均セル電圧低下速度を求めた。その結果、発電開始時のセル電圧は本発明材１では約０．６４Ｖ、本発明材２では約０．６７Ｖ、比較材１、２では約０．６２Ｖ、比較材３では約０．６５Ｖであった。また、平均セル電圧低下速度を比較すると、本発明材１は０．２３×１０−４Ｖｈ−１、本発明材２は０．２５×１０−４Ｖｈ−１、比較材１は０．１９×１０−４Ｖｈ−１、比較材２は０．２９×１０−４Ｖｈ−１、比較材３は０．４６×１０−４Ｖｈ−１であった。 FIG. 1 shows the power generation test results up to 500 hours in each cell in which the inventive materials 1 and 2 and the comparative materials 1 to 3 are separately incorporated. The cell voltage and the average cell voltage drop rate at the start of power generation of Invention Materials 1 and 2 and Comparative Materials 1 to 3 are linearly approximated from the graph shown in FIG. Asked. As a result, the cell voltage at the start of power generation is about 0.64 V for the invention material 1, about 0.67 V for the invention material 2, about 0.62 V for the comparison materials 1 and 2, and about 0.65 V for the comparison material 3. there were. Further, when the average cell voltage drop rate is compared, the present material 1 is 0.23 × 10 −4 Vh −1 , the present material 2 is 0.25 × 10 −4 Vh −1 , and the comparative material 1 is 0.19. × 10 −4 Vh −1 , Comparative Material 2 was 0.29 × 10 −4 Vh −1 , and Comparative Material 3 was 0.46 × 10 −4 Vh −1 .

比較材１と２の電圧低下速度を比較すると、酸素低減化処理を施した比較材1は酸素低減処理をしていない比較材２よりも優れていた。セパレータの薄肉化によるスタックのコンパクト化を目的とし、比較材１および比較材２に対して酸素低減処理および結晶粒微細加工を施した本発明材１および２は、酸素低減化処理をしていない比較材３に対して電圧低下速度が優れていた。 Comparing the voltage drop rates of the comparative materials 1 and 2, the comparative material 1 subjected to the oxygen reduction treatment was superior to the comparative material 2 not subjected to the oxygen reduction treatment. The present invention materials 1 and 2 in which oxygen reduction treatment and crystal grain fine processing have been performed on the comparative material 1 and the comparison material 2 for the purpose of compacting the stack by thinning the separator are not subjected to oxygen reduction treatment. The voltage drop rate was superior to that of Comparative Material 3.

また、発電試験後にそれぞれのセルを分解して、本発明材１、２および比較材１〜３の各セパレータの表面を光学顕微鏡で観察した。その結果、本発明材１、２はアノード側およびカソード側の両極においてセパレータ部品の表面には腐食痕は観察されなかった。また、比較材１〜３のアノード側のセパレータ部品の表面も同様に腐食痕は観察されなかった。これに対して、比較材２、３のカソード側のセパレータ部品の表面全体は均一に腐食していた。 Moreover, each cell was decomposed | disassembled after the electric power generation test, and the surface of each separator of this invention materials 1 and 2 and the comparative materials 1-3 was observed with the optical microscope. As a result, according to the present invention materials 1 and 2, corrosion marks were not observed on the surfaces of the separator parts on both the anode side and the cathode side. Similarly, no corrosion marks were observed on the surfaces of the anode-side separator parts of Comparative Materials 1 to 3. In contrast, the entire surfaces of the separator parts on the cathode side of the comparative materials 2 and 3 were uniformly corroded.

これは、素材であるステンレス鋼中の酸化物系介在物の影響が原因の一つとして考えられる。すなわち、本発明材１、２および比較材１は酸素低減化処理したことにより腐食の起点となるステンレス鋼中の酸化物系介在物が比較材２の約５０％まで低減した。このことにより、発電試験中にステンレス鋼中の不純物の溶出が抑制され、本発明材１、２および比較材１と比較材２、３の耐食性に差異がでたものと思われる。 This is considered to be one of the causes due to the influence of oxide inclusions in the stainless steel material. That is, the inventive materials 1 and 2 and the comparative material 1 were reduced in oxygen to about 50% of the oxide-based inclusions in the stainless steel as a starting point of corrosion due to the oxygen reduction treatment. Thus, it is considered that the elution of impurities in the stainless steel was suppressed during the power generation test, and that the corrosion resistances of the inventive materials 1 and 2 and the comparative material 1 and the comparative materials 2 and 3 were different.

以上より、本発明材（板厚＝０．０７ｍｍ）は比較材（板厚＝０．１０ｍｍ）よりも板厚を薄くしても耐食性を保った状態で同等の発電効率を得ることができるので、所定の容量のセルスタック内にはより多い枚数のセパレータを収容することができる。その結果、燃料電池として高電圧を出力することが可能になる。もしくは同じ電圧を出力するための燃料電池スタックの容量を小型化することができる。 As described above, the material of the present invention (plate thickness = 0.07 mm) can obtain the same power generation efficiency while maintaining the corrosion resistance even if the plate thickness is made thinner than the comparative material (plate thickness = 0.10 mm). A larger number of separators can be accommodated in a cell stack having a predetermined capacity. As a result, it becomes possible to output a high voltage as a fuel cell. Alternatively, the capacity of the fuel cell stack for outputting the same voltage can be reduced.

次に、本発明材１および２の表面に電着処理を行った供試材（以下、「本発明材３、４」という）をそれぞれ別個のセルに組み込んで発電試験を行った。同時に、比較材として樹脂含浸黒鉛材（比較材４）をセパレータとして組込だセルの発電試験も行ったので、それらの試験結果について図面を用いて説明する。   Next, a power generation test was performed by incorporating the test materials (hereinafter referred to as “present invention materials 3 and 4”), which were subjected to electrodeposition treatment on the surfaces of the present invention materials 1 and 2, into separate cells. At the same time, since a power generation test was performed on a cell incorporating a resin-impregnated graphite material (Comparative Material 4) as a comparative material as a separator, the test results will be described with reference to the drawings.

本発明材３、４は表面処理として泳動電着法によりステンレス鋼の表面にＴｉＮ粒子を含有するＳＢＲを付着させることによりＧＤＬとの接触抵抗の改善を行ったものである。具体的には、本発明材１および２に対してＴｉＮ粒子を含むＳＢＲ分散浴（分散媒：２−プロパノール、導電性粒子：ＴｉＮ（平均粒径は５０ｎｍ）０．０５０ｗｔ％、ゴム系バインダー：ＳＢＲバインダー０．０７４ｗｔ％）中に浸漬させた状態で、対極にＳＵＳ３０４鋼を使用して所定の電圧を印加した。 Inventive materials 3 and 4 are obtained by improving the contact resistance with GDL by attaching SBR containing TiN particles to the surface of stainless steel by electrophoretic deposition as a surface treatment. Specifically, an SBR dispersion bath containing TiN particles with respect to the inventive materials 1 and 2 (dispersion medium: 2-propanol, conductive particles: TiN (average particle size is 50 nm) 0.050 wt%, rubber-based binder: A predetermined voltage was applied to the counter electrode using SUS304 steel while being immersed in 0.074 wt% of SBR binder.

次に、本発明材１および２を大気中にて３５３Ｋ（８０℃）の温度で加熱した後、４５３Ｋ（１８０℃）まで昇温して再度加熱することで乾燥させて、本発明材３、４を作製した。ステンレス鋼の表面にＴｉＮ粒子を含むＳＢＲを付着させた状態の一例（ＳＥＭ写真）を図２に示す。 Next, after heating this invention material 1 and 2 at the temperature of 353K (80 degreeC) in air | atmosphere, it was dried by heating up to 453K (180 degreeC) and heating again, this invention material 3, 4 was produced. An example (SEM photograph) of a state in which SBR containing TiN particles is attached to the surface of stainless steel is shown in FIG.

本実施例の試験条件は、実施例１と同様に表２に示す条件で行った。本発明材１〜４、比較材４をそれぞれ別個に組み込んだ各セルにおける５００時間までの発電試験結果を図３に示す。   The test conditions of this example were the same as those of Example 1 and the conditions shown in Table 2. FIG. 3 shows the power generation test results up to 500 hours in each cell in which the inventive materials 1 to 4 and the comparative material 4 are separately incorporated.

本発電試験中のセル電圧の経時変化を図３に示すグラフより直線近似し、本発明材１〜４および比較材４をセパレータとして組込だセルの発電開始時のセル電圧を比較した結果、本発明材１では約０．６４Ｖ、本発明材２では約０．６７Ｖ、本発明材３では約０．６６Ｖ、本発明材４では約０．６６Ｖ、比較材４では０．６６Ｖであった。 The time-dependent change of the cell voltage during the power generation test was linearly approximated from the graph shown in FIG. 3, and the results of comparing the cell voltage at the start of power generation of the cells incorporating the present invention materials 1 to 4 and the comparative material 4 as separators, Inventive Material 1 was about 0.64 V, Invented Material 2 was about 0.67 V, Invented Material 3 was about 0.66 V, Invented Material 4 was about 0.66 V, and Comparative Material 4 was 0.66 V. .

本発明材１および２に表面処理を行なうことで発電開始時のセル電圧がベンチマークとなる比較材４（樹脂含浸黒鉛材）と同等となった。また、発電試験後に各セルを分解して、セパレータの表面を光学顕微鏡で観察した。その結果、本発明材３、４の表面のＴｉＮ粒子を具備するＳＢＲは発電試験中に剥離することなく、ステンレス鋼の表面における腐食も確認されなかった。 By subjecting the inventive materials 1 and 2 to surface treatment, the cell voltage at the start of power generation became equivalent to the comparative material 4 (resin-impregnated graphite material) serving as a benchmark. Moreover, each cell was decomposed | disassembled after the electric power generation test, and the surface of the separator was observed with the optical microscope. As a result, the SBR having TiN particles on the surfaces of the inventive materials 3 and 4 did not peel during the power generation test, and no corrosion on the surface of the stainless steel was confirmed.

Claims (5)

ステンレス鋼製の固体高分子形燃料電池用セパレータ素材であって、
前記ステンレス鋼の全結晶粒に対して、結晶粒径が３．０μｍ以下である結晶粒の占める割合は６０％以上であることを特徴とする固体高分子形燃料電池用セパレータ部品。 A separator material for a polymer electrolyte fuel cell made of stainless steel,
A separator for a polymer electrolyte fuel cell, wherein a ratio of crystal grains having a crystal grain size of 3.0 μm or less to all the crystal grains of the stainless steel is 60% or more. 前記ステンレス鋼はオーステナイト系ステンレス鋼であって、
かつ前記オーステナイト系ステンレス鋼に含有される酸素量は質量％で３０ｐｐｍ以下であることを特徴とする請求項１に記載の固体高分子形燃料電池用セパレータ部品。 The stainless steel is an austenitic stainless steel,
2. The separator component for a polymer electrolyte fuel cell according to claim 1, wherein the amount of oxygen contained in the austenitic stainless steel is 30 ppm or less by mass%. 請求項１または請求項２のいずれかの請求項に記載の固体高分子形燃料電池用セパレータ部品の表面には、窒化チタン粒子を含有するスチレンブタジエンゴムが具備されていることを特徴とする固体高分子形燃料電池用セパレータ部品。 A solid polymer fuel cell separator component according to any one of claims 1 and 2, wherein the surface of the separator component for a polymer electrolyte fuel cell is provided with a styrene butadiene rubber containing titanium nitride particles. Separator parts for polymer fuel cells. 前記ステンレス鋼の表面を、常圧の雰囲気下で８０℃以上２２０℃以下の温度範囲で加熱した状態で前記スチレンブタジエンゴムを付着させることを特徴とする固体高分子形燃料電池用セパレータ部品の製造方法。   Production of a separator component for a polymer electrolyte fuel cell, wherein the styrene butadiene rubber is adhered in a state where the surface of the stainless steel is heated in a temperature range of 80 ° C. or higher and 220 ° C. or lower in an atmosphere of normal pressure. Method. 前記ステンレス鋼の表面を８０℃以上１００℃以下の温度範囲で加熱した後、１５０℃以上２２０℃以下の温度範囲まで昇温することで前記ステンレス鋼の表面を段階的に加熱することを特徴とする請求項４に記載の固体高分子形燃料電池用セパレータ部品の製造方法。   The surface of the stainless steel is heated in a temperature range of 80 ° C. or more and 100 ° C. or less, and then heated to a temperature range of 150 ° C. or more and 220 ° C. or less to heat the surface of the stainless steel stepwise. The manufacturing method of the separator component for polymer electrolyte fuel cells of Claim 4.
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