TW200843180A - Alloy coating film for metal separator of fuel cell, method for producing the same, sputtering target material, metal separator and fuel cell - Google Patents

Alloy coating film for metal separator of fuel cell, method for producing the same, sputtering target material, metal separator and fuel cell Download PDF

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TW200843180A
TW200843180A TW096149425A TW96149425A TW200843180A TW 200843180 A TW200843180 A TW 200843180A TW 096149425 A TW096149425 A TW 096149425A TW 96149425 A TW96149425 A TW 96149425A TW 200843180 A TW200843180 A TW 200843180A
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fuel cell
film
metal
separator
metal element
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TW096149425A
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Chinese (zh)
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Toshiki Sato
Jun Suzuki
Yoshinori Ito
Hirotaka Ito
Shinichi Tanifuji
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Kobe Steel Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

Disclosed is an alloy coating film for metal separators of fuel cells, which is characterized by containing at least one noble metal element selected from Au and Pt and at least one non-noble metal element selected from the group consisting of Ti, Zr, Nb, Hf and Ta, and having a thickness of not less than 2 nm. This alloy coating film for metal separators of fuel cells is further characterized in that the noble metal element/non-noble metal element atomic ratio is from 35/65 to 95/5. Also disclosed are a method for producing an alloy coating film for metal separators of fuel cells, a sputtering target material, a metal separator and a fuel cell. The alloy coating film for metal separators of fuel cells is excellent in corrosion resistance and productivity, while having low contact resistance.; This alloy coating film for metal separators of fuel cells is capable of maintaining a low contact resistance for a long time even in a corrosive atmosphere.

Description

200843180 九、發明說明 【發明所屬之技術領域】 本發明係關於一種於例如行動電話、個人電腦等之攜 帶機器、家庭用燃料電池、燃料電池汽車等所使用之燃料 電池的金屬隔板用合金被膜、其製造方法及隔板用標靶材 f 料、以及金屬隔板及燃料電池。 B 【先前技術】 燃料電池係使固體高分子電解質膜以陽極電極與陰極 電極挾住者作爲單節電池（s i n g 1 e c e 11 )，介由被稱爲隔 板（或二極板）之電極而使單節電池複數個重疊而構成。 構成此燃料電池用之隔板的材料中係要求低的接觸電 阻、於隔板之使用中可長期間維持其低接觸電阻之特性。 因此，自以往，加工性及強度之面亦一倂與鋁合金、不鏽 鋼、鎳合金、鈦合金等之金屬材料的適用被硏究。 #' 又，燃料電池內係被稱爲pH爲2〜4之酸性的腐蝕環 境’在隔板所使用之材料中係亦被要求即使在酸性環境中 亦可維持低的接觸電阻之耐鈾性（耐酸性）。 不鏽鋼或鈦等之金屬係因於表面形成被動態被膜而顯 示良好的耐鈾性，故硏究作爲燃料電池之隔板用材料。然 而，此被動態被膜係電阻大，故若使用不鏽鋼或鈦等之金 屬直接作爲燃料電池之隔板，恐在酸性環境中形成於其表 面之被動態被膜，導電性明顯劣化。因此，即使使用當初 之接觸電阻低，在作爲隔板之使用中亦無法長期間維持其 200843180 低的接觸電阻，而接觸電阻隨著時間變高而招致電.流損失 的問題仍存在。又’材料受腐飩溶出之金屬離子使電解質 膜劣化等的問題亦存在。 對於如此之問題’爲抑制接觸電阻之增加而經長期間 而維持導電性，從以往已提出各種之金屬隔板。例如，已 提出：對於不鏽鋼或鈦等之金屬隔板表面實施鍍金者（專 利文獻1 )、除去由不鏽鋼、鈦等所構成之基板表面的氧 化被膜後，附著貴金屬或貴金屬合金者（專利文獻2 )、 於不鏽鋼基板表面形成耐酸性金屬皮膜，於其上形成貴金 屬被膜者（專利文獻3 )等。 專利文獻1 :特開平1 0-2289 1 4號公報 專利文獻2:特開2001-6713號公報 專利文獻3 :特開200 1 -93 53 8號公報 【發明內容】 (發明之揭示） 然而，於特開平1 0-2289 1 4號公報、特開200 1 -67 1 3 號公報或特開2 0 0 1 - 9 3 5 3 8號公報記載之發明的隔板材， 係無法作爲隔板之使用期間中藉自基板之被膜的剝離或金 屬溶出而揮發充分的耐蝕性，無法降低接觸電阻，進一步 使用當初即使顯示低的接觸電阻，亦於燃料電池內之腐蝕 環境中亦無法經長期間維持其低的接觸電阻等的缺點仍存 在。又藉以往之電鍍等形成被膜時，爲除去被動態被膜係 耗時間，必須煩雜的步驟，故生產性降低之缺點亦存在。 -6 ~ 200843180 因此，本發明之課題在於提供一種係耐蝕性優，且接 觸電阻低，即使在腐蝕環境中亦可經長期間維持其低的接 觸電阻，進一步生產性優之燃料電池之金屬隔板用合金被 膜、其製造方法及濺鍍用標靶材料、以及金屬隔板及燃料 電池。 亦即，本發明係關於以下之（1 )〜（1 8 )。 (1 ) 一種燃料電池之金屬隔板用合金被膜，其特徵在於 :含有選自Au及Pt之至少一種貴金屬元素、與選自由Ti 、Zr、Nb、Hf及Ta所構成之群中的至少一種之非貴金屬 兀素，目U述貴金屬兀素/非貴金屬兀素之含有比率就原子 比爲3 5/6 5〜9 5/5，膜厚爲2nm以上。 (2 ) —種燃料電池之金屬隔板用合金被膜之製造方法， 其特徵在於含有： 設置步驟，其係於實施濺鍍法之裝置的腔室內設置金屬基 板； 成膜步驟，其係於在前述設置步驟中所設置之前述金屬基 板表面的至少一部份藉灑鍍法而形成合金被膜，該合金被 膜係使選自Au及Pt之至少一種貴金屬元素、與選自由Ti 、Zr、Nb、Hf及Ta所構成之群中的至少一種之非貴金屬 元素，以貴金屬元素/非貴金屬元素之含有比率就原子比 爲35/6 5〜9 5/5之比率含有，且膜厚爲2nm以上。 (3)如前述（2)之燃料電池之金屬隔板用合金被膜之製 造方法，其中前述成膜步驟後，進一步含有使形成前述合 金被膜之金屬基板進行熱處理之熱處理步驟。200843180 IX. EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to an alloy coating for a metal separator for a fuel cell used in a portable device such as a mobile phone or a personal computer, a fuel cell for a home battery The manufacturing method and the target material for the separator, the metal separator and the fuel cell. B [Prior Art] The fuel cell system uses a solid polymer electrolyte membrane as a single cell (sing 1 ece 11 ) with an anode electrode and a cathode electrode, and is referred to as an electrode called a separator (or a diode). The single-cell battery is stacked in plural numbers. Among the materials constituting the separator for the fuel cell, low contact resistance is required, and the low contact resistance can be maintained for a long period of time during use of the separator. Therefore, from the past, the application of the metallurgical properties and the strength of the metal materials such as aluminum alloy, stainless steel, nickel alloy, and titanium alloy has been studied. #' Also, the inside of the fuel cell is called a corrosive environment with an acidic pH of 2 to 4. 'The material used in the separator is also required to maintain low contact resistance and uranium resistance even in an acidic environment. (acid resistance). A metal such as stainless steel or titanium exhibits good uranium resistance due to the formation of a dynamic film on the surface, so that it is a material for a separator for a fuel cell. However, since the dynamic film is made to have a large electric resistance, if a metal such as stainless steel or titanium is used as a separator for a fuel cell, the dynamic film formed on the surface thereof in an acidic environment may be deteriorated. Therefore, even if the initial contact resistance is low, it is not possible to maintain its low contact resistance of 200843180 for a long period of time as a separator, and the contact resistance is called with time. The problem of flow loss still exists. Further, there is a problem that the material is deteriorated by the metal ions eluted by the rot. In order to maintain the conductivity for a long period of time in order to suppress an increase in contact resistance, various metal separators have been proposed from the past. For example, it has been proposed to apply a noble metal or a precious metal alloy to a surface of a metal separator such as stainless steel or titanium (Patent Document 1), and to remove an oxide film on the surface of a substrate made of stainless steel or titanium (Patent Document 2) An acid-resistant metal film is formed on the surface of the stainless steel substrate, and a noble metal film is formed thereon (Patent Document 3). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The partition plate of the invention described in the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. During the use period, the peeling of the film from the substrate or the elution of the metal is sufficient to volatilize the corrosion resistance, and the contact resistance cannot be lowered. Further, even if the contact resistance is low at the beginning, the corrosion environment in the fuel cell cannot be maintained for a long period of time. The disadvantages of its low contact resistance and the like still exist. Further, when a film is formed by conventional plating or the like, it is necessary to remove the time required for the dynamic film to be removed, so that the productivity is lowered. -6 ~ 200843180 Therefore, an object of the present invention is to provide a metal separator of a fuel cell which is excellent in corrosion resistance and low in contact resistance, and can maintain its low contact resistance over a long period of time even in a corrosive environment. An alloy coating for a sheet, a method for producing the same, a target material for sputtering, a metal separator, and a fuel cell. That is, the present invention relates to the following (1) to (1 8). (1) An alloy film for a metal separator for a fuel cell, comprising at least one noble metal element selected from the group consisting of Au, Pt, and at least one selected from the group consisting of Ti, Zr, Nb, Hf, and Ta The non-noble metal ruthenium, the content ratio of the noble metal ruthenium/non-noble metal ruthenium is 3 5/6 5 to 9 5/5, and the film thickness is 2 nm or more. (2) A method for producing an alloy film for a metal separator for a fuel cell, comprising: a step of providing a metal substrate in a chamber in which a sputtering method is applied; and a film forming step of At least a portion of the surface of the metal substrate provided in the setting step is formed by sputtering to form an alloy film, the alloy film being at least one noble metal element selected from the group consisting of Au and Pt, and selected from the group consisting of Ti, Zr, Nb, The non-noble metal element of at least one of the groups of Hf and Ta is contained in a ratio of a noble metal element/non-precious metal element in an atomic ratio of 35/6 5 to 9 5/5, and a film thickness of 2 nm or more. (3) The method for producing an alloy film for a metal separator for a fuel cell according to the above aspect, wherein the film forming step further comprises a heat treatment step of heat-treating the metal substrate on which the alloy film is formed.

200843180 (4 )如前述（3 )之燃料電池之金屬隔板， 造方法，其中在前述熱處理步驟中之熱 1 5 0 〜8 0 0 〇C ° (5 )如前述（4 )之燃料電池之金屬隔板用 造方法，其中使前述熱處理在具有2·1χ104 壓的環境下實施。 (6 )如前述（2 )之燃料電池之金屬隔板用 造方法，其中前述成膜步驟係使前述金 150〜800°C而進行。 (7) —種燃料電池用金屬隔板用合金被膜 :以如前述（2 )〜（6 )中任一項之製造方名 (8 ) —種燃料電池用金屬隔板，其特徵在 板之表面形成如前述（1 )〜（7 )中任一項 合金被膜而得到。 (9 )如前述（8 )之燃料電池用金屬隔板， 形成凹部，該凹部係於其表面之至少一部β 之氣體流路。 (1 0 )如前述（8 )或（9 )項之燃料電池月 中前述金屬基板爲由選自鈦、鈦基合金、裔 不鏽鋼所構成之群中的至少一種的金屬所構 (1 1 ) 一種燃料電池用金屬隔板之製造方名 含有= 設置步驟，其係於實施濺鍍法之裝置的腔| I合金被膜之製 處理的溫度爲 丨合金被膜之製 P a以下之氧分 丨合金被膜之製 屬基板加熱至 ，其特徵在於 δ製造。 :於：於金屬基 丨之金屬隔板用 前述金屬基板 >形成流通氣體 目金屬隔板，其 3、銘基合金及 成。 ^，其特徵在於 【內設置金屬基 200843180 成膜步驟，其係於在前述設置步驟中所設置之前述金屬基 板表面藉濺鍍法形成合金被膜，該合金被膜係含有選自 Au及Pt之至少一種貴金屬元素、與選自由Ti、Zr、Nb、 Hf及Ta所構成之群中的至少一種之非貴金屬元素，前述 貴金屬元素/非貴金屬元素之含有比率就原子比爲 3 5/65〜95/5，膜厚爲2nm以上。 (1 2 )如前述（1 1 )之燃料電池用金屬隔板之製造方法， 其中前述設置步驟之前，含有形成步驟，前述形成步驟係 前述金屬基板之表面的至少一部份形成用以形成流通氣體 之氣體流路之凹部。 (1 3 )如前述（1 1 )或（1 2 )之燃料電池用金屬隔板之製 造方法，其中前述成膜步驟後，進一步含有使形成前述合 金被膜之金屬基板進行熱處理之熱處理步驟。 (1 4 )如前述（13)之燃料電池用金屬隔板之製造方法， 其中前述熱處理的溫度爲150〜800°C。 (1 5 )如前述（1 4 )之燃料電池用金屬隔板之製造方法， 其中使前述熱處理在具有2.1xl04Pa以下之氧分壓的環境 下實施。 (1 6 )如前述（1 1 )之燃料電池用燃料電池之金屬隔板之 製造方法，其中前述成膜步驟係使前述金屬基板加熱至 150〜800°C而進行。 (1 7 ) —種燃料電池，其特徵在於：具備以如前述（8 )〜 (1 0 )項中任一項之燃料電池用金屬隔板。 (1 8 ) —種濺鍍用標靶材料，係使用於燃料電池之金屬隔 200843180 板用合金被膜之製造，其特徵在於：由選自Au及Pt之至 少一種貴金屬元素、與選自由Ti、Zr、Nb、Hf及Ta所構 成之群中的至少一種之非貴金屬元素所構成，兩者之原子 比（貴金屬元素/非貴金屬元素）爲3 5/65〜95/5。 在前述（1)之燃料電池之金屬隔板用合金被膜中， 係即使在被稱爲貴金屬之金屬元素中，於氧化環境中在其 表面不形成氧化被膜的元素之Au及Pt、與選自Ti、Zr、 Nb、Hf及Ta之耐腐蝕性優且不易與氧、氮、碳鍵結之非 貴金屬元素合金化，俾可抑制昂貴之貴金屬的使用量，同 時並防止Au或Pt之凝集，又提昇與金屬基板之密著性， 使貴金屬元素/非貴金屬元素之含有比率形成於特定的範 圍，即使於高溫、酸性環境中亦可發揮長期間良好的導電 性與耐腐蝕。又’藉由使膜厚爲2nm以上，俾形成燃料電 池用金屬隔板之合金被膜，可防止針孔之形成以免基板露 出，可抑制電阻大之被動態被膜的形成。又，亦可防止來 自針孔部份之基材的腐蝕或金屬溶出。 在前述（2)之燃料電池之金屬隔板用合金被膜的製 造方法中，藉成膜步驟而對金屬基板之表面的至少一部份 以濺鍍法，俾形成被膜，該被膜係含有選自Au及Pt之至 少一種貴金屬元素、與選自由Ti、Zr、Nb、Hf及Ta所構 成之群中的至少一種之非貴金屬元素，可抑制昂貴之貴金 屬的使用量，同時亦可以低成本製造兼備導電性與耐腐蝕 性之金屬隔板用合金被膜。又，藉濺鍍法而進行前述成膜 步驟，俾可安定地抑制所形成之合金被膜中之貴金屬元素 -10- 200843180 與非貴金屬元素的含有比率外，尙可形成2nm左右極薄被 膜均一且緻密的膜。 若依前述（5 )之燃料電池之金屬隔板用合金被膜的 製造方法，使熱處理步驟中之氧分壓依合金被膜中之貴金 屬元素與非貴金屬元素的含有比率，調整成2. lxl 04p a以 下的氧分壓，俾可提高所得到之合金被膜的導電性與耐鈾 性。 若依前述（6 )之燃料電池之金屬隔板用合金被膜的 製造方法，一邊使金屬基板加熱至150〜800 °C —邊成膜， 俾可在同一裝置中同時進行成膜與熱處理，故可更提昇生 產性。 前述（7 )之燃料電池之金屬隔板用合金被膜，係以 前述（2)至前述（6)之任一者的製造方法製造，故可抑 制昂貴之貴金屬的使用量，同時可兼備導電性與耐蝕性又 亦可以低成本製造。 前述（8 )之燃料電池之金屬隔板係藉由具有金屬基 板之表面所形成之前述（1)或前述（7)的金屬隔板用合 金被膜，俾即使於高溫、酸性環境中亦可發揮長期間良好 的導電性與耐蝕性。 前述（9 )之燃料電池之金屬隔板係係藉由具有層合 於具有形成氣體流路之凹部的金屬基板表面之至少一部份 之前述金屬隔板用合金被膜，俾即使於高溫、酸性環境中 亦可發揮長期間良好的導電性與耐蝕性。 前述（1 〇 )之燃料電池用金屬隔板中此等之鈦、鈦基 -11 - 200843180 合金'鋁、鋁基合金及不鏽鋼係因耐蝕性高、加工性亦優 ，故適宜作爲用以形成燃料電池用金屬隔板的金屬材料。 前述（in之燃料電池用金屬隔板之製造方法中於金 屬基板之表面藉前述成膜步驟以形成合金被膜，可製造導 電性與耐蝕性優之金屬隔板。 前述（1 2 )之燃料電池用金屬隔板之製造方法中係於 具有形成氣體流路之凹部的金屬基板表面之至少一部份形 成金屬隔板用合金被膜，故即使爲形成凹部之金屬基板， 即使在高溫、酸性環境中亦可製造能發揮長期間良好之導 電性與耐飩性的金屬隔板。 若依前述（1 3 )或（1 4 )之燃料電池用金屬隔板的製 造方法，藉如此之前述熱處理步驟，熱處理形成合金被膜 之金屬基板，可進一步製造導電性與腐飩性優之金屬隔板 〇 若依前述（1 5 )之燃料電池用金屬隔板的製造方法， 依照合金被膜中之貴金屬元素與非貴金屬元素的含有比率 ，調整2.1x1 04pa以下之氧分壓，可提高所得到之合金被 膜的導電性與腐蝕性。 若依前述（1 6 )之燃料電池用金屬隔板的製造方法， 一邊使金屬基板加熱至150〜800 °C —邊成膜，俾可在同一 裝置中同時進行成膜與熱處理，故可更提昇生產性。 前述（1 7 )之燃料電池係因使用前述（8 )至前述（ 1 〇 )之任一者的之燃料電池用金屬隔板，故具有良好之腐 蝕性及導電性。 -12- 200843180 前述（1 8 )之濺鍍用標靶材料係可使用於前述燃料電 '池的金屬隔板用合金被膜之製造而使所希望之被膜組成的 合金被膜安定以高的生產性進行製造。 本發明之燃料電池之金屬隔板用合金被膜係因接觸電 阻低’導電性優。又，因腐蝕性優，即使低的接觸電阻在 腐蝕環境中經長期間亦可維持。 又，本發明之金屬隔板用合金被膜的製造方法係藉由 使用合金標靶之濺鍍法以形成前述導電性與腐蝕性優之金 屬隔板用合金被膜，俾可以良好之被膜組成再現性與良好 的生產性進行製造。 又，本發明之燃料電池用金屬隔板係藉由於表面具有 前述金屬隔板用合金被膜，俾導電性與腐鈾性優，且進一 步生產性優。 進一步，本發明之燃料電池用金屬隔板的製造方法係 藉由使用合金標靶之濺鍍法於金屬基板之表面形成前述金 屬隔板用合金被膜，俾導電性與腐蝕性優，可以良好之被 膜組成再現性與良好的生產性進行製造。 進一步又，本發明之燃料電池係使用前述之金屬隔板 ，故具有良好之腐飩性與導電性。 又，本發明之濺鍍標靶材料係當前述之燃料電池之金 屬隔板用合金被膜之製造時，而使所希望之被膜組成的合 金被膜安定以高的生產性進行製造。 (用以實施發明之最佳形態） -13- 200843180 以下，適當參照圖面而說明有關本發明之燃料電池之 金屬隔板用合金被膜、其製造方法及燃料電池用金屬隔板 及燃料電池的實施形態、於前述合金被膜的成膜所使用的 濺鍍標靶材料。於參照之圖面中，圖1係說明本發明之燃 料電池用金屬隔板的製造方法之步驟的流程圖。圖2中（ A)係本發明之燃料電池用金屬隔板的平面圖，（B )係其 一部份之擴大截面圖。圖3係表示使用本發明之燃料電池 用金屬隔板的燃料電池之一部份展開的狀態圖。圖4係說 明接觸電阻之測定方法的圖。 本發明之燃料電池之金屬隔板用合金被膜（參照圖2 (B )、以下，有時亦僅稱爲「合金被膜」）3係以含有 貴金屬元素與非貴金屬元素的合金所構成。 形成合金被膜3之貴金屬元素係在氧化環境中於其表 面未形成氧化被膜，而即使氧化環境下亦可良好地保持導 電性，且爲腐蝕性優之金屬，故可使用至少一種選自 Au 及Pt。 又，非貴金屬元素係於其表面形成被動態被膜而顯示 高耐鈾性，且爲易與氧、氮、碳鍵結之金屬，故可使用至 少一種選自由Ti、Zr、Nb、Hf及Ta所構成之群。含有具 有此等高耐蝕性之非貴金屬元素與前述貴金屬元素之合金 被膜3係兼備導電性與耐蝕性，又，使用至少一種選自由 Ti、Zr、Nb、Hf及Ta，以減少貴金屬元素之使用量，同 時並可提昇與金屬基板2之密著性，防止被膜之凝集。 在本發明之燃料電池的金屬隔板用合金被膜3中，前 -14- 200843180 述貴金屬元素/非貴金屬元素的含有比率就原子比爲35/65 〜95/5，更宜爲原子比爲35/65〜85/15，最宜爲35/65〜 8 0 / 2 0。一般，於基板上只形成很薄A u或P t之貴金屬的 被膜時，在高溫、酸性環境中（例如80°C、Imol/升的硫 酸中）引起貴金屬的凝集，基板之一部份會露出而引起基 板的溶解，不久恐貴金屬的被膜從基板剝離。然而，在本 發明之合金被膜3中，係Au或Pt之貴金屬元素與高耐蝕 性之非貴金屬元素進行合金化，以防止含有Au或Pt的被 膜之凝集，在高溫、酸性環境中亦可發揮長期間良好的導 電性與耐蝕性。 貴金屬元素之含有比率就原子比超過9 5 %時，無法充 分抑制在高溫、酸性環境中的凝集，而若長期間曝露於高 溫、酸性環境中，引起合金被膜3之凝集而金屬基板2曝 出，有金屬基板2之溶解或合金被膜3之剝離之虞。又， 於表面或其周邊之合金被膜3與金屬基板2之界面形成厚 的氧化被膜，恐導電性劣化。另外，貴金屬元素之含有比 率就原子比未達35%之情形，未引起合金被膜3之凝集， 但於合金被膜3之表面所形成之氧化被膜的面積率或其厚 度會增加，恐導電性劣化。 本發明之金屬隔板用合金被膜3之膜厚需要2nm以上 。合金被膜3之膜厚未達2nm時’係於合金被膜3形成許 多針孔，故產生金屬基板2露出之部份，使用來作爲隔板 時於露出部份的表面或其周邊的合金被膜3與金屬基板2 之界面形成厚的氧化被膜’恐導電性劣化。又’合金被膜 -15- 200843180 3之膜厚更宜爲5nm以上，尤宜爲7nm以上。另外，合金 被膜3之膜厚的上限並無特別限定，但從成膜所需之時間 與成本方面宜爲5 00mm以下者。 本發明之燃料電池的金屬隔板用合金被膜之製造方法 ，係含有在本發明之燃料電池用金屬隔板的製造方法中之 設置步驟S2、與成膜步驟S3，更佳係其後後含有熱處理 步驟S4之方法。此成膜步驟S3及熱處理步驟S4係說明 有關在後述之燃料電池用金屬隔板之製造方法。 其次，說明有關本發明之燃料電池用金屬隔板之製造 方法。 如圖1所示般，本發明之燃料電池用金屬隔板1之製 造方法係含有設置步驟S2、與成膜步驟S3，更佳係其後 後含有熱處理步驟S4之方法。又，於設置步驟S2之前亦 可含有形成步驟S 1。以下，係說明有關含有形成步驟S 1 之燃料電池用金屬隔板1之製造方法。 形成步驟S 1係金屬基板2之表面的至少一部份形成 用以形成流通氣體或空氣等之氣體的氣體流路2 1 (參照圖 2 ( A ))之凹部。此處，所謂金屬基板2之表面係成爲金 屬基板2之外側的面，包含所謂表面、背面、側面。在形 成步驟S1之前，宜使金屬基板2之縱寬、橫寬、厚等預 先設定之尺寸或形狀。 此處，於金屬基板2之表面的至少一部份用以形成流 通流路2 1之裝置係無特別限定，可適宜使用能發揮特定 目的之以往公知的裝置。 -16- 200843180 又，不進行此形成步驟S1時係可製造於表面不形成 凹部’表面成爲平面之金屬基板的燃料電池用金屬隔板。 金屬基板2係可使用於ns Η 4600所規定之1種或4 種的純鈦或 Ti-Al、Ti-Ta、Ti-6A1-4V、Ti-Pd 等之 Ti 合 金、SUS3 04、SUS3 16等的不鏽鋼、純鋁、鋁合金等之鋁 材等。就成本方面係鋁材或不鏽鋼優異，但就耐飩性方面 係以純鈦或鈦合金爲有利。又，可防止僅從不鏽鋼溶出之 Fe離子所造成的燃料電池之固體高分子膜的劣化，宜使用 純鈦或鈦合金。 設置步驟S2係使於形成步驟S 1形成凹部之金屬基板 2設置於實施濺鍍法之裝置的腔室內之特定位置之步驟。 又，當然前述本發明之濺鍍標靶材料亦於此設置步驟S 1 中設置於該裝置之腔室內的特定位置。 成膜步驟S3係形成凹部，於設置步驟S2實施濺鍍法 之裝置的腔室內所設置之金屬基板2表面（金屬基板2之 表面全體或表面之一部份），形成合金被膜3(圖2(B) 參照）之步驟，該合金被膜3係含有選自Au及Pt之至少 一種貴金屬元素、與選自Ti、Zr、Nb、Hf及Ta之至少一 種之非貴金屬元素。又，在本發明之燃料電池用金屬隔板 之製造方法中係於合金被膜之成膜步驟S3之前’亦可除 去源自於被動態被膜等之金屬基板2的製造方法所形成之 表面層。 於此成膜步驟S3中，含有前述貴金屬元素與非貴金 屬元素之合金被膜3的成膜，係藉濺鍍來實施。在濺鍍法 -17- 200843180 之成膜係具有如下優點：可於常溫至數百度之 ，可減少對金屬基板2造成之損傷’均一地使 安定而成膜。 又，藉濺鍍法而可於廣的範圍自由地控制 元素與非貴金屬元素之含有比率，同時並亦可 膜厚。例如即使電鍍亦可形成合金被膜3 ’但 元素與非貴金屬元素之組合而於其含有比率有 鍍液中之貴金屬元素與非貴金屬元素之濃度管 之缺點存在，工業上缺乏實用性。另外’在濺 比率亦無限制，可容易地變化。 又如前述般，前述貴金屬元素與非貴金屬 比率或膜厚在廣範圍進行控制而濺鍍，硏究所 被膜的被膜組成，決定前述貴金屬元素與非貴 較佳的含有比率後，製作其含有比率之合金標 用於濺鍍俾得到安定之組成的合金被膜3。 依此合金被膜3之濺鍍法的成膜步驟S3 基板2加熱至150〜800°C，同時並可形成合途 依此方法，在同一裝置內可同時地進行熱處理 會提昇。 依此濺鍍法之成膜係宜在氬氣環境 0.133〜1.33Pa的條件下實施。 又，在此合金被膜3中，有關其合金被膜 構造係雖未充分揭示，但組成爲與合金被膜3 元素/非貴金屬元素的含有比率所示的比率（ 溫度來進行 緻密的被膜 前述貴金屬 容易地控制 藉由貴金屬 限制，或電 理很煩雜等 鍍法中含有 元素之含有 得到之合金 金屬元素之 靶材料而使 係宜使金屬 :被膜3。若 ，故生產性 :下、壓力 3內之組織 中之貴金屬 以下，合金 -18- 200843180 被膜3之平均組成）同等之合金相外，尙可含有貴金屬元 素較合金被膜3之平均組成更濃化之相（貴金屬元素濃化 相）、或非貴金屬元素濃化之相（非貴金屬元素濃化相） 〇 非貴金屬元素濃化相露出於表面時，其部份係發揮從 表面至內部形成氧化被膜（含有被動態被膜）而優之耐飩 性。此部份係認爲導電性差，但耐触性優且很難形成氧化 被膜之貴金屬元素濃化相露出表面，俾可確保導電性，可 兼備耐蝕性與導電性。又，貴金屬元素濃化相係很難凝集 之非貴金屬元素濃化相或埋入於其所形成之氧化被膜中， 故認爲凝集、很難脫落、可長期間維持導電性者。 本發明之合金被膜3係即使至成膜步驟S3亦具有充 分之導電性與耐蝕性，但加上熱處理步驟S4，可進一步 得到優之特性。 熱處理步驟S4之熱處理的溫度宜爲150°C以上。使 存在於合金被膜3與金屬基板2之間的被膜態等的界面層 薄膜化，俾導電性提高，又，合金被膜3之膜應力緩和， 及/或於合金被膜3與金屬基板2之間引起原子之擴散， 故密著性提高。進一步，金屬基板2之端面部等之合金被 3於很難附著之部份形成氧化被膜，其部份之耐蝕性會 提高之優點存在。 另外，若熱處理溫度超過8 00 °C，認爲形成於非貴金 屬元素濃化相之表面的氧化被膜於合金被膜3表面占有的 面積率會增加，且其厚度增加，俾導電性劣化，及/或因 -19- 200843180 合金被膜3凝集，故耐蝕性劣化等之理由，無法得到優之 接觸電阻。因此，熱處理步驟S4之熱處理溫度宜爲1 5 0 °C〜8 00 °C。又，熱處理溫度更宜爲150°C〜650°C，最宜爲 200〜650〇C。 在本發明中，於金屬基板2與合金被膜3之間所形成 的層（界面層（未圖示））兼備密著性、導電性、耐餓性 ，可得到同樣的效果。 又，形成本發明之合金被膜3的非貴金屬（Ti、Zr、 Nb、Hf、Ta)係除氧外，尙易與氮或碳等鍵結，故即使於 金屬基板2之表面即使存在碳化物或氮化物，與被動態被 膜存在之情形同樣地可得到優異之密著性。 亦即，於本發明中，前述界面層爲含有1種以上選自 Zr、Hf、Nb、Ta、Ti之元素的氧化物（不含被動態被膜 )、氮化物、氧氮化物、氧碳化物、碳氮化物、氧碳氮化 物、以及選自此等之中的2種以上的物質之混合物時可得 到同樣地效果。如此之界面層係以PVD法（濺鍍法、真 空蒸鍍法、離子電鍍法等）形成成爲界面層之皮膜後，可 以形成合金被膜3來形成。又，界面層係即使源自於合金 被膜3之成膜前的金屬基板2之表面層，亦可得到樣的效 果。如此之表面層係亦可爲如以下之方法所形成的表面層 ，即例如藉由熱間精加工或冷間精加工而得到的方法；進 行酸洗而形成被動態被膜之方法；藉陽極氧化而形成陽極 氧化被膜之方法；大氣中或氧存在之環境中的熱處理形成 氧化被膜之方法；其他之一般表面處理方法。 -20- 200843180 又，無此等氧化被膜等之界面層時，當然亦可得到優 異之導電性、密著性、耐蝕性。又，成膜前之金屬基板2 的表面爲平滑者抑制針孔的產生，可更提昇密著性與耐久 性。 熱處理步驟S4係宜在具有2.1 xl 04Pa以下之氧分壓（ 在大氣環境下之氧分壓以下）之環境下進行。又，在本發 明中氧分壓謂在進彳了熱處理步驟S4之熱處理爐內中的氧 占有之壓力（又，在本發明中大氣的組成係氮：氧約以4 :1所構成）。例如，合金被膜3之膜厚比較薄至3〜5 nm 時，氧分壓在大氣環境中之氧分壓以下的環境中宜進行 1〜15分左右的短時間之熱處理，若合金被膜3爲50nm以 上，即使以大氣環境熱處理1〇〜50分左右，亦可得到良好 的結果。又，前述貴金屬元素之含有量就原子比使約5至 2 5 %的範圍之合金被膜3以高溫度（例如5 00 °C )進行熱 處理時，氧分壓愈低，可得到更優之導電性與耐蝕性等， 宜藉合金被膜3之膜厚與貴金屬元素之含有比率適當調整 氧分壓、溫度、時間。又，即使爲低的氧分壓條件下，現 實上可到達之真空度中，係非貴金屬元素濃化相露出於合 金被膜3之表面時，因於其表面形成氧化被膜，故合金被 膜係可確保導電性，並發揮耐鈾性，氧分壓宜爲13.33Pa 以下，更宜爲1.33Pa以下。 此熱處理步驟S4係可藉由使用能減壓爐內之電爐或 瓦斯爐等之以往習知的熱處理爐來進行。 本發明之製造方法所製造之燃料電池隔板1係如前述 -21 - 200843180 般，因於金屬基板2之表面具有滿足導電性與耐蝕性之合 金被膜3’故可適宜使用來作爲燃料電池用金屬隔板。 其次’詳細說明有關前述本發明之燃料電池用金屬隔 板的製造方法所製造之本發明的燃料電池用隔板1。 如圖2 ( A )及（B )所示般，本發明之燃料電池用金 屬隔板1係具有於金屬基板2的表面形成前述本發明之金 屬隔板用的合金被膜3之構造，該金屬基板2係形成用以 於表面之至少一部份形成流通氣體之氣體流路2 1的凹部 〇 其次’參照適當圖面而說明有關本發明之燃料電池。 如圖3所示般，本發明之燃料電池20係具有使具有 如下之單節電池1 0複數節電池重疊的構造者，該單節電 池10係於2片的碳布33、33之間挾住固體高分子膜32， 進一步，具有於碳布3 3、3 3之外側層合前述之本發明之 燃料電池用金屬隔板3 1、3 1的構造。 此燃料電池20係例如準備特定數鈦或鈦合金製之金 屬基板2，準備此特定數之金屬基板2形成所謂縱寬 95.2mmx橫寬95.2mmx厚19 mm之特定尺寸，同時並於其 基板2之表面的中央部藉機械加工或蝕刻等而形成例如溝 寬0.6mm、溝深〇.5mm之凹部，形成如圖3之形狀的氣體 流路2 1。繼而，使用形成凹部之金屬基板2，進行前述成 膜步驟S3及熱處理步驟S4，可製造特定數燃料電池用金 屬隔板1。 然後，如圖3所示般，使用所製造特定數之燃料電池 -22- 200843180 用金屬隔板3 1例如2片而使形成氣體流路2 1之面對向而 配置，於形成氣體流路2 1之各別的面，配置用以使氣體 於膜上均一地擴散之碳布33等所構成的氣體擴散層，於 一者之氣體擴散層與另一者之氣體擴散層之間，使鉑觸媒 塗佈於表面之固體高分子膜3 2挾住而形成單節電池1 0。 同樣地做法而複數製作之單節電池1 〇進行複數層合而節 電池堆疊（未圖示），再於燃料電池進行必需之其他的特 定零件之安裝、及連接等，可製作具有良好的耐蝕性及導 電性之本發明的燃料電池（固體高分子型燃料電池）20。 又，於燃料電池20所使用之固體高分子膜32係若爲 具有使於陰極所生成之質子朝陽極移動之作用的膜，無特 別限制，而可使用，例如可適宜使用於具有礪基之氟系的 高分子膜。 如此做法所製作之燃料電池20係對配置作爲陽極之 燃料電池用金屬隔板31介由氣體流路而導入燃料氣體（ 例如，純度99.999%之氫氣），對配置作爲陰極之燃料電 池用金屬隔板3 1介由氣體流路而導入空氣。此時，燃料 電池20係宜使全體加熱保溫至80 °C左右，而藉由使前述 之氫氣及空氣通過被加溫之水中’俾使露點溫度調整至8 〇 °C。又，然料氣體（氫氣）及空氣係宜爲例如以2026hP a (2氣壓）之壓力導入。 燃料電池20係藉由如此做法而對陽極導入氫氣，藉 氣體擴散層對於固定高分子膜32而均一地供給，於該固 體高分子膜32產生下述式（1)之反應。 -23- 200843180 2H + + 2e' ... ( 1 ) 另外燃料電池20係藉由對陰極導入空氣，藉 散層對於固定高分子膜32而均一地供給，於該固 子膜32產生下述式（2)之反應。 4H + + 02 + 4e-~>2Η20·_. (2) 如此’於固體高分子膜32產生前述式（1 )、 之反應，理論上可得到約1.2V的電壓。 此處，本發明之燃料電池2 0係如前述般，使 明之燃料電池用金屬隔板1，故與使用習知之金屬 板之燃料電池相較，而可發揮良好的耐蝕性及導電个 本發明之濺鍍用標靶材料（未圖示）係用以形 燃料電池之金屬隔板用合金被膜3，故使選自Au万 至少一種貴金屬元素、與選自由Ti、Zr、Nb、Hf；g 構成之群中的至少一種之非貴金屬元素，以兩者之 (貴金屬元素/非貴金屬元素）成爲3 5/65〜95/5之 成者。進行小規模性之生產時係於貴金屬元素之標 合非貴金屬元素之晶片，或於非貴金屬元素之標靶 貴金屬元素的晶片而使用來作爲濺鍍用標靶材料， 形成改變組成之合金被膜，但在此方法中係有時所 被膜的合金組成的再現性變差。因此，於金屬隔板 氣體擴 體高分 (2 ) 用本發 製的隔 成前述 L Pt之 C Ta所 原子比 方式構 靶上貼 上貼合 俾亦可 成膜之 用合金 -24- 200843180 被膜3之量產時形成大量之合金被膜，故實驗上進行組成 硏究後’宜製作所希望之組成的合金標靶而形成合金被膜 3 〇 又，藉由構成合金之元素的種類，係有時合金標靶材 料組成與合金膜組成產生偏差。認爲此係依元素之種類於 濺鍍中各原子從標靶材料之表面朝向金屬基板2而移動之 間，於與Ar離子之碰撞進行散射而出現於金屬基板2之 外爲主要的理由。然而，於本發明所選擇之貴金屬元素與 非貴金屬元素係很難引起如此之散射，可得到與標靶材料 相同之組成的合金被膜3。 本發明之濺鍍用標靶材料係可藉由粉末冶金法或熔融 法而製造，但於組合之貴金屬元素與非貴金屬元素之融點 或比重有很大的差時，或很難互相固溶之元素的組合時係 以熔融法進行製造乃很難，故宜以粉末冶金法進行製造。 其時係可以「原料粉末混合—模塡充—模脫氣-> HIP (熱 間靜水壓沖壓）燒結-> 脫模θ鍛造θ壓延θ機械加工'^於 堆積板之接合」之製程進行製造。 若使用如此之濺鍍用標靶材料，可形成膜組成安定之 合金被膜3，並可提供性能安定之燃料電池的金屬隔板3 1 及燃料電池20。 【實施方式】 實施例 有關本發明之燃料電池的金屬隔板用合金被膜及其製 -25- 200843180 造方法、金屬隔板以及燃料電池，使滿足本發明之要 實施例與不滿足本發明之要件的比較例對比而具體地 <實施例1〜8、比較例1〜7 > 由JIS Η 4600所規定之1種的純欽所構成之鈦製 (20x50x0· 15mm、算術平均粗度（Ra) =15nm)以丙 音波洗淨後，安裝於腔室內之基板台。繼而，就合金 形成用標靶而言，於貴金屬元素之標靶貼合非貴金屬 之晶片’或於非貴金屬元素之標靶貼合貴金屬元素之 (使用任一者係依貴金屬元素與非貴金屬元素之含有 (在表1〜5中係表示爲「貴金屬元素/非貴金屬元素 有比率」）（原子比）而異）之標靶貼合於腔室內之 後，使腔室內排氣至0.00133Pa以下之真空。 此處’基板之表面粗度係使用表面粗度測定裝 Dektak 6M )而測定，從以測定所得到之粗度曲線選！ jczm之範圍而算出Ra。 其次’使Ar氣體導入於腔室內，調整腔室內之 成爲0.266Pa。其後，對標靶施加輸出100W、 13·5 6Ηζ的RF (頻率）而產生氬電漿以進行濺鍍，於 之一面形成所希望組成之合金被膜。進一步翻起基板 同樣之方法成膜。 此處’改變用於標靶或晶片之金屬元素種，以改 金被膜中之貴金屬元素與非貴金屬元素之組合，又， 件的 說明 基板 酮超 被膜 元素 晶片 比率 之含 電極 置（ p 20 壓力 頻率 基板 ，以 變合 改變 -26- 200843180 貼黏於標靶之晶片的片數，以改變合金被膜中之貴金屬元 素與非貴金屬元素的含有比率，又，改變成膜時間而控制 膜厚，形成表1所75之合金被膜。 繼而，形成合金被膜之基板於〇.〇〇665Pa之真空環境 中以5 0 0 °C、5分鐘進行熱處理而得到試驗板。 有關所得到之試驗板’測定合金被膜中之貴金屬元素 與非貴金屬元素之含有比率（原子比）、合金被膜之膜厚 、及熱處理前之接觸電阻。又，就在酸性環境中之耐蝕性 的指標而言，測定硫酸浸瀆後之接觸電阻。 貴金屬元素與非貴金屬元素之含有比率的測定 使所得到之試驗板的合金被膜中之貴金屬元素與非貴 金屬元素之含有比率（原子比）藉由ICP ( Inductively C 〇 u p 1 e d P1 a s m a :感應結合電漿）發光分析法來測定。此 處，使用可使合金被膜與基板一起溶解之酸溶液而溶解試 驗板，測定所得到之溶解液中之貴金屬元素與非貴金屬元 素的濃度，使其和規格化爲100%而算出合金被膜中之貴 金屬元素與非貴金屬元素之含有比率（原子比）。又，非 貴金屬元素爲Ti時係於Si晶圓基板形成合金膜而進行測 定。 熱處理前後之接觸電阻的測定 有關於金屬基板之表面形成合金被膜後之試驗板（熱 處理前）、與形成合金被膜後，進行熱處理之試驗板（熱 -27- 200843180 處理後），使用圖4所示之接觸電阻測定裝置，而測定熱 處理前後之接觸電阻。亦即，使試驗板4〗之雙面以2片 之碳布42、42挾住，進一步，於其外側以接觸面積lcm2 之2片的銅電極43、43挾住以荷重98N(10Kgf)加壓， 使用直流電流電源44而通入1A之電流，以電壓計4 5測 定碳布4 2、4 2之間所施加之電壓，求出接觸電阻。 硫酸水溶液浸漬後之接觸電阻 於試驗板4 1，使未形成其端面部份等之合金被膜的部 份遮敝而浸漬於8 5 C之硫酸水溶液（1 〇 m m ο 1 /升）5 0 0小 時後，從硫酸水溶液取出，洗淨，乾燥後，除去遮蔽材後 ’以與則述同樣之方法測定接觸電阻。使硫酸水溶液浸漬 後之接觸電阻爲1 5m Ω · cm2以下的情形爲合格。 各試驗板之合金被膜中的貴金屬元素與非貴金屬元素 之含有比率（原子比）及合金被膜之膜厚、及熱處理前後 之接觸電阻及硫酸水溶液浸漬後之接觸電阻之測定結果表 不於表1中。 -28- 200843180 〔表1〕 合金羅 接觸電阻(πιΩ · cm2) 貴金屬種 非貴金屬種 貴金屬元素/非貴金 屬元素之含有比率 (原子比） 膜厚 (nm) 熱處理前 熱處理後 硫酸水溶 液浸漬後 實施例1 Au Ta 75/25 3 4.2 3.0 5.1 實施例2 Au Ta 65/35 10 5.2 3.1 6.4 實施例3 Au Ta 40/60 30 3.3 3.3 3.9 實施例4 An Nb 55/45 10 6.0 4.2 6.9 實施例5 Au Nb 85/15 5 3.8 2.9 4.1 實施例6 Pt Ta 50/50 50 4.3 4.3 4.7 實施例7 Pt Ta 90/10 5 4.8 3.8 5.2 實施例8 Pt Nb 40/60 20 3.5 3.6 5.1 比較例1 Au Ta 30/70 10 4.3 7.2 220 比較例2 Au Ta 60/40 1 7.2 26.7 221.5 比較例3 Au Ta 98/2 5 4.0 2.8 Ϊ9.8 比較例4 Pt Nb 75/25 1 10.2 77.5 253.0 比較例5 Pt Nb 98/2 10 4.1 2.9 51.5 比較例6 Ag Nb 70/30 10 6.5 5.0 99.3 比較例7 Ag Ta 55/45 10 10.0 9.6 125.6200843180 (4) The metal separator for a fuel cell according to the above (3), wherein the heat in the heat treatment step is 1 5 0 to 8 0 0 〇 C ° (5) as in the fuel cell of the above (4) A method for producing a metal separator, wherein the aforementioned heat treatment is carried out in an environment having a pressure of 2·1χ104. (6) The method for producing a metal separator for a fuel cell according to the above (2), wherein the film forming step is carried out by subjecting the gold to 150 to 800 °C. (7) An alloy film for a metal separator for a fuel cell, which is a metal separator for a fuel cell according to any one of the above (2) to (6), characterized in that The surface is obtained by forming an alloy film according to any one of the above (1) to (7). (9) The metal separator for a fuel cell according to the above (8), wherein the concave portion is formed in a gas flow path of at least one portion of the surface of the β. (10) The fuel cell of the above (8) or (9), wherein the metal substrate is made of a metal selected from the group consisting of titanium, a titanium-based alloy, and a stainless steel (1 1 ) A manufacturing method of a metal separator for a fuel cell includes a setting step for a cavity of a device for performing a sputtering method. The temperature at which the alloy film is processed is a bismuth alloy film, and an oxygen bifurcation alloy of P a or less. The substrate of the film is heated to a characteristic of δ. ::: The metal substrate for the metal substrate is formed of the metal substrate > a gas-forming metal separator is formed, and the alloy is formed. ^, characterized in that [the inner metal substrate 200843180 film forming step is performed by forming a alloy film by sputtering on the surface of the metal substrate provided in the foregoing setting step, the alloy film containing at least at least selected from Au and Pt a noble metal element and a non-noble metal element selected from at least one selected from the group consisting of Ti, Zr, Nb, Hf and Ta, wherein the ratio of the noble metal element to the non-precious metal element is 3 5/65 to 95/ 5, the film thickness is 2 nm or more. (1) The method for producing a metal separator for a fuel cell according to the above (1), wherein the step of forming includes a forming step of forming at least a portion of a surface of the metal substrate to form a flow. a recess of the gas flow path of the gas. (1) The method for producing a metal separator for a fuel cell according to the above (1 1) or (1), wherein after the film forming step, a heat treatment step of heat-treating the metal substrate on which the alloy film is formed is further included. (1) The method for producing a metal separator for a fuel cell according to the above (13), wherein the temperature of the heat treatment is 150 to 800 °C. (1) The method for producing a metal separator for a fuel cell according to the above (14), wherein the heat treatment is carried out in an environment having an oxygen partial pressure of 2.1 x 10 Pa or less. (1) The method for producing a metal separator for a fuel cell fuel cell according to the above (1), wherein the film forming step is performed by heating the metal substrate to 150 to 800 °C. (1) A fuel cell for a fuel cell according to any one of the items (8) to (10) above. (18) A sputtering target material for use in a metal separator for a fuel cell, in which the alloy film for a metal separator 200843180 is used, characterized by comprising at least one noble metal element selected from the group consisting of Au and Pt, and selected from the group consisting of Ti, A non-noble metal element of at least one of the group consisting of Zr, Nb, Hf, and Ta, and the atomic ratio (precious metal element/non-precious metal element) of the two is 3 5/65 to 95/5. In the alloy film for a metal separator of the fuel cell according to the above (1), even in a metal element called a noble metal, Au and Pt which are elements which do not form an oxide film on the surface in an oxidizing atmosphere, and are selected from Ti, Zr, Nb, Hf and Ta are excellent in corrosion resistance and are not easily alloyed with oxygen, nitrogen and carbon-bonded non-precious metal elements, which suppress the use of expensive precious metals and prevent agglomeration of Au or Pt. Further, the adhesion to the metal substrate is improved, and the content ratio of the noble metal element/non-precious metal element is formed in a specific range, and excellent electrical conductivity and corrosion resistance can be exhibited for a long period of time even in a high-temperature and acidic environment. Further, by forming the alloy film of the metal separator for the fuel cell by the film thickness of 2 nm or more, the formation of the pinhole can be prevented to prevent the substrate from being exposed, and the formation of the dynamic film having a large electric resistance can be suppressed. Further, corrosion or metal elution of the substrate from the pinhole portion can be prevented. In the method for producing an alloy film for a metal separator for a fuel cell according to the above (2), at least a part of the surface of the metal substrate is subjected to a sputtering method to form a film by sputtering, and the film is selected from the group consisting of At least one noble metal element of Au and Pt, and a non-noble metal element selected from at least one selected from the group consisting of Ti, Zr, Nb, Hf, and Ta, can suppress the use amount of expensive precious metal, and can also be manufactured at low cost. An alloy coating for a metal separator having electrical conductivity and corrosion resistance. Further, the film forming step is carried out by a sputtering method, and the content ratio of the noble metal element-10-200843180 to the non-noble metal element in the formed alloy film can be stably suppressed, and the extremely thin film of about 2 nm can be formed uniformly. Dense film. Lxl 04p a. The ratio of the ratio of the precious metal element to the non-precious metal element in the alloy film is adjusted to 2. lxl 04p a according to the method of manufacturing the alloy film for the metal separator of the fuel cell of the above (5). The following partial pressure of oxygen, 俾 can improve the conductivity and uranium resistance of the obtained alloy coating. According to the method for producing an alloy film for a metal separator for a fuel cell according to the above (6), the metal substrate is heated to 150 to 800 ° C to form a film, and the film can be simultaneously formed and heat treated in the same apparatus. Can improve productivity. The alloy film for a metal separator for a fuel cell according to the above (7) is produced by the method of any one of the above (2) to (6), so that the amount of expensive precious metal can be suppressed and the conductivity can be obtained. It can also be manufactured at low cost with corrosion resistance. The metal separator of the fuel cell according to the above (8) is an alloy coating for a metal separator of the above (1) or (7) which is formed on the surface of a metal substrate, and can be used even in a high-temperature and acidic environment. Good electrical conductivity and corrosion resistance over a long period of time. The metal separator of the fuel cell of the above (9) is an alloy coating for the metal separator having at least a portion laminated on a surface of a metal substrate having a concave portion forming a gas flow path, even at a high temperature and acidity. Good electrical conductivity and corrosion resistance over a long period of time can also be achieved in the environment. In the above-mentioned (1 〇) metal separator for a fuel cell, such titanium, titanium base-11 - 200843180 alloy 'aluminum, aluminum-based alloy and stainless steel are suitable for forming because of high corrosion resistance and excellent workability. A metal material for a metal separator for a fuel cell. In the method for producing a metal separator for a fuel cell, the metal film is formed on the surface of the metal substrate by the film forming step to form an alloy separator. The fuel cell of the above (1 2) can be produced. In the method for producing a metal separator, the alloy film for the metal separator is formed on at least a portion of the surface of the metal substrate having the concave portion forming the gas flow path, so that even in the high temperature and acidic environment, the metal substrate for forming the concave portion is formed. It is also possible to produce a metal separator which can exhibit good electrical conductivity and stagnation resistance for a long period of time. According to the method for producing a metal separator for a fuel cell according to the above (1 3) or (14), by the aforementioned heat treatment step, By heat-treating the metal substrate forming the alloy film, it is possible to further produce a metal separator having excellent conductivity and corrosion resistance, and a method for producing a metal separator for a fuel cell according to the above (1), according to a noble metal element and a non-metal element in the alloy film The content ratio of the precious metal element is adjusted to a partial pressure of oxygen of 2.1×1 04 Pa or less to improve the conductivity and corrosivity of the obtained alloy film. In the method for producing a metal separator for a fuel cell, the metal substrate is heated to 150 to 800 ° C to form a film, and the film formation and heat treatment can be simultaneously performed in the same apparatus, so that productivity can be further improved. The fuel cell according to the above (1) to (1) to the fuel cell metal separator according to any one of the above (1), has good corrosiveness and electrical conductivity. -12- 200843180 1 8) The target material for sputtering can be manufactured by using an alloy film for a metal separator for the fuel cell, and the alloy film having a desired film composition can be stabilized and manufactured with high productivity. The alloy film for a metal separator for a fuel cell is excellent in electrical conductivity due to low contact resistance, and is excellent in corrosion resistance, and even a low contact resistance can be maintained in a corrosive environment for a long period of time. The method for producing an alloy film is to form an alloy film for a metal separator excellent in conductivity and corrosion by using a sputtering method using an alloy target, and a good film composition reproducibility and good production can be obtained. Further, the metal separator for a fuel cell of the present invention has an excellent alloying property and uranium property by having an alloy coating film for the metal separator on the surface thereof, and further excellent in productivity. Further, the fuel cell of the present invention is used. In the method for producing a metal separator, the alloy film for the metal separator is formed on the surface of the metal substrate by sputtering using an alloy target, and the conductive property and the corrosion property are excellent, and the film composition reproducibility and good production can be improved. Furthermore, the fuel cell of the present invention uses the aforementioned metal separator to have good corrosion resistance and electrical conductivity. Moreover, the sputtering target material of the present invention is the metal separator of the aforementioned fuel cell. When the alloy film for a sheet is produced, the alloy film of the desired film composition is stabilized and manufactured with high productivity. (Best Mode for Carrying Out the Invention) -13-200843180 Hereinafter, an alloy film for a metal separator for a fuel cell of the present invention, a method for producing the same, a metal separator for a fuel cell, and a fuel cell will be described with reference to the drawings. An embodiment of a sputtering target material used for forming a film of the alloy film. In the drawings, Fig. 1 is a flow chart showing the steps of a method for producing a metal separator for a fuel cell of the present invention. Fig. 2 (A) is a plan view showing a metal separator for a fuel cell of the present invention, and (B) is an enlarged sectional view showing a part thereof. Fig. 3 is a view showing a state in which a part of a fuel cell using a metal separator for a fuel cell of the present invention is developed. Fig. 4 is a view showing a method of measuring contact resistance. The alloy film for a metal separator of the fuel cell of the present invention (see Fig. 2(B) and hereinafter, simply referred to as "alloy film") 3 is composed of an alloy containing a noble metal element and a non-precious metal element. The noble metal element forming the alloy coating film 3 does not form an oxide film on the surface thereof in an oxidizing atmosphere, and can maintain good conductivity even in an oxidizing atmosphere, and is a metal having excellent corrosion properties, so at least one selected from the group consisting of Au and Pt. Further, the non-precious metal element is formed on the surface thereof to exhibit a high uranium resistance by the dynamic film, and is a metal which is easily bonded to oxygen, nitrogen, and carbon, so at least one selected from the group consisting of Ti, Zr, Nb, Hf, and Ta can be used. The group formed. The alloy film 3 containing the non-precious metal element having such high corrosion resistance and the noble metal element has both conductivity and corrosion resistance, and at least one selected from the group consisting of Ti, Zr, Nb, Hf and Ta is used to reduce the use of precious metal elements. The amount can be increased while maintaining adhesion to the metal substrate 2 to prevent agglomeration of the film. In the alloy film 3 for a metal separator for a fuel cell of the present invention, the content ratio of the noble metal element/non-precious metal element in the former-14-200843180 is 35/65 to 95/5, and more preferably an atomic ratio of 35. /65~85/15, most preferably 35/65~8 0 / 2 0. Generally, when only a thin film of a noble metal of Au or Pt is formed on a substrate, agglomeration of a noble metal is caused in a high-temperature, acidic environment (for example, 80 ° C, 1 mol/liter of sulfuric acid), and a part of the substrate is Exposed to cause dissolution of the substrate, and soon the film of the noble metal is peeled off from the substrate. However, in the alloy film 3 of the present invention, a noble metal element of Au or Pt is alloyed with a non-precious metal element having high corrosion resistance to prevent agglomeration of a film containing Au or Pt, and can also be exhibited in a high temperature and acidic environment. Good electrical conductivity and corrosion resistance over a long period of time. When the atomic ratio of the noble metal element is more than 5%, the aggregation in a high-temperature and acidic environment cannot be sufficiently suppressed, and if it is exposed to a high-temperature, acidic environment for a long period of time, the alloy film 3 is agglomerated and the metal substrate 2 is exposed. There is a dissolution of the metal substrate 2 or a peeling of the alloy film 3. Further, a thick oxide film is formed on the interface between the alloy film 3 and the metal substrate 2 on the surface or the periphery thereof, and the conductivity is deteriorated. In addition, when the atomic ratio of the noble metal element is less than 35%, the alloy film 3 is not aggregated, but the area ratio of the oxide film formed on the surface of the alloy film 3 or its thickness is increased, and the conductivity is deteriorated. . The film thickness of the alloy film 3 for a metal separator of the present invention needs to be 2 nm or more. When the film thickness of the alloy film 3 is less than 2 nm, a large number of pinholes are formed in the alloy film 3, so that the exposed portion of the metal substrate 2 is generated, and the alloy film 3 on the surface of the exposed portion or the periphery thereof is used as the separator. A thick oxide film is formed on the interface with the metal substrate 2, and the conductivity is deteriorated. Further, the film thickness of the alloy film -15-200843180 3 is more preferably 5 nm or more, and particularly preferably 7 nm or more. Further, the upper limit of the film thickness of the alloy film 3 is not particularly limited, but it is preferably 500 mm or less from the time and cost required for film formation. The method for producing an alloy film for a metal separator of a fuel cell according to the present invention includes the step S2 of forming the metal separator for a fuel cell of the present invention and the film forming step S3, and more preferably thereafter The method of heat treatment step S4. This film forming step S3 and the heat treatment step S4 describe a method of manufacturing a metal separator for a fuel cell which will be described later. Next, a method of manufacturing the metal separator for a fuel cell of the present invention will be described. As shown in Fig. 1, the method for producing a metal separator 1 for a fuel cell of the present invention comprises a step S2 of forming and a film forming step S3, and more preferably a method of including a heat treatment step S4. Further, the forming step S1 may be included before the setting step S2. Hereinafter, a method of manufacturing the metal separator 1 for a fuel cell including the formation step S1 will be described. At least a portion of the surface of the step S1-based metal substrate 2 is formed to form a concave portion of the gas flow path 2 1 (see Fig. 2 (A)) for forming a gas such as a gas or air. Here, the surface of the metal substrate 2 is a surface on the outer side of the metal substrate 2, and includes a so-called surface, a back surface, and a side surface. Before the step S1 is formed, it is preferable to set the size or shape of the metal substrate 2 in a predetermined width, width, thickness, and the like. Here, the apparatus for forming the flow channel 21 in at least a part of the surface of the metal substrate 2 is not particularly limited, and a conventionally known device which can exhibit a specific purpose can be suitably used. Further, when the step S1 is not performed, the metal separator for a fuel cell which is formed on the surface of the recessed portion and which is a flat metal substrate can be manufactured. The metal substrate 2 can be used for one or four kinds of pure titanium or Ti-Al, Ti-Ta, Ti-6A1-4V, Ti-Pd or the like Ti alloy, SUS3 04, SUS3 16 or the like specified in ns Η 4600. Stainless steel, pure aluminum, aluminum alloy and other aluminum materials. It is excellent in terms of cost in terms of aluminum or stainless steel, but it is advantageous in terms of scratch resistance in terms of pure titanium or titanium alloy. Further, it is possible to prevent deterioration of the solid polymer film of the fuel cell caused by only Fe ions eluted from the stainless steel, and it is preferable to use pure titanium or a titanium alloy. The setting step S2 is a step of providing the metal substrate 2 forming the concave portion in the step S1 to a specific position in the chamber of the apparatus for performing the sputtering method. Further, of course, the sputtering target material of the present invention is also disposed at a specific position in the chamber of the apparatus in the step S1. In the film forming step S3, a concave portion is formed, and the surface of the metal substrate 2 (one part of the surface of the metal substrate 2 or a part of the surface) provided in the chamber of the sputtering apparatus is placed in the step S2 to form the alloy coating 3 (Fig. 2). (B) In the step of the reference, the alloy film 3 contains at least one noble metal element selected from the group consisting of Au and Pt, and a non-precious metal element selected from at least one of Ti, Zr, Nb, Hf and Ta. Further, in the method for producing a metal separator for a fuel cell of the present invention, the surface layer formed by the method for producing the metal substrate 2 such as a dynamic film or the like may be removed before the film formation step S3 of the alloy film. In the film formation step S3, the film formation of the alloy film 3 containing the noble metal element and the non-noble metal element is carried out by sputtering. The film formation system of the sputtering method -17-200843180 has the advantage that it can reduce damage to the metal substrate 2 at normal temperature to several hundred degrees, and uniformly forms a film. Further, by the sputtering method, the content ratio of the element to the non-precious metal element can be freely controlled in a wide range, and the film thickness can also be obtained. For example, even if electroplating can form a combination of an alloy film 3' but a combination of an element and a non-precious metal element in a concentration tube having a ratio of a noble metal element and a non-precious metal element in the plating solution, there is a lack of practicality in the industry. In addition, the sputtering ratio is not limited and can be easily changed. Further, as described above, the ratio of the noble metal element to the non-precious metal or the film thickness is controlled to be sputtered in a wide range, and the film composition of the film is investigated, and the content ratio of the noble metal element to the non-expensive ratio is determined, and the content ratio thereof is determined. The alloy is marked with an alloy coating 3 of a composition which is stabilized by sputtering. According to the film formation step S3 of the sputtering method of the alloy film 3, the substrate 2 is heated to 150 to 800 ° C, and at the same time, a combined path can be formed. According to this method, heat treatment can be simultaneously performed in the same apparatus. The film formation by the sputtering method is preferably carried out under the conditions of an argon atmosphere of 0.133 to 1.33 Pa. In addition, the alloy film 3 is not sufficiently disclosed in the alloy film structure, but the composition is a ratio shown by the content ratio of the alloy film 3 element/non-precious metal element (the temperature is high, and the dense metal is easily formed. Controlling the target material of the alloy metal element obtained by the inclusion of the element in the plating method by the restriction of the noble metal, or the metal: the film 3. If so, the productivity: the structure under the pressure 3 In the middle of the precious metal, alloy -18- 200843180 is the average composition of the film 3), the bismuth may contain a phase in which the precious metal element is more concentrated than the average composition of the alloy film 3 (precious metal element concentrated phase), or a non-precious metal Element-concentrated phase (non-precious metal element-concentrated phase) When a non-precious metal element is concentrated on the surface, the part is formed to form an oxidized film (containing a dynamic film) from the surface to the inside to provide excellent sturdiness. In this part, it is considered that the conductivity is poor, but the contact resistance is excellent, and it is difficult to form a concentrated surface of the noble metal element of the oxidized film to expose the surface, and the conductivity can be ensured, and both corrosion resistance and electrical conductivity can be obtained. Further, in the case where the precious metal element-concentrated phase is difficult to aggregate, the non-precious metal element is concentrated or embedded in the oxide film formed therein, and it is considered that aggregation is difficult to fall off, and conductivity can be maintained for a long period of time. The alloy film 3 of the present invention has sufficient conductivity and corrosion resistance even in the film formation step S3, but further excellent characteristics can be obtained by adding the heat treatment step S4. The temperature of the heat treatment in the heat treatment step S4 is preferably 150 ° C or higher. Thinning the interface layer such as the film state between the alloy film 3 and the metal substrate 2, the conductivity of the crucible is improved, and the film stress of the alloy film 3 is moderated, and/or between the alloy film 3 and the metal substrate 2. Causes the diffusion of atoms, so the adhesion is improved. Further, the alloy of the end surface portion or the like of the metal substrate 2 is formed by forming an oxide film on a portion which is hard to adhere, and the corrosion resistance of the portion thereof is improved. In addition, when the heat treatment temperature exceeds 800 ° C, it is considered that the area ratio of the oxide film formed on the surface of the non-precious metal element concentrated phase to the surface of the alloy film 3 increases, and the thickness thereof increases, and the conductivity of the crucible deteriorates, and / Or because the alloy film 3 of -19-200843180 is aggregated, the corrosion resistance is deteriorated, and the like, and excellent contact resistance cannot be obtained. Therefore, the heat treatment temperature in the heat treatment step S4 is preferably from 150 ° C to 800 ° C. Further, the heat treatment temperature is more preferably from 150 ° C to 650 ° C, most preferably from 200 to 650 ° C. In the present invention, the layer (interfacial layer (not shown)) formed between the metal substrate 2 and the alloy film 3 has both adhesiveness, electrical conductivity, and starvation resistance, and the same effect can be obtained. Further, the non-noble metal (Ti, Zr, Nb, Hf, Ta) forming the alloy film 3 of the present invention is desulfurized, and is easily bonded to nitrogen or carbon, so that even if a carbide is present on the surface of the metal substrate 2 Or the nitride can obtain excellent adhesion as in the case of being present in the dynamic film. That is, in the present invention, the interface layer is an oxide containing one or more elements selected from the group consisting of Zr, Hf, Nb, Ta, and Ti (excluding a dynamic film), a nitride, an oxynitride, and an oxycarbide. The same effect can be obtained when a carbonitride, an oxycarbonitride, and a mixture of two or more kinds selected from these are used. When such an interface layer is formed into a film of the interface layer by a PVD method (sputtering method, vacuum deposition method, ion plating method, or the like), the alloy film 3 can be formed. Further, even if the interface layer is derived from the surface layer of the metal substrate 2 before the film formation of the alloy film 3, an effect can be obtained. Such a surface layer may also be a surface layer formed by the following method, that is, a method obtained by, for example, hot-finishing or cold-finishing; a method of pickling to form a dynamic film; A method of forming an anodized film; a method of forming an oxide film by heat treatment in the atmosphere or in the presence of oxygen; and other general surface treatment methods. -20- 200843180 In addition, when there is no such interface layer such as an oxide film, it is a matter of course that excellent conductivity, adhesion, and corrosion resistance can be obtained. Further, the surface of the metal substrate 2 before film formation is smooth, and the occurrence of pinholes is suppressed, and the adhesion and durability can be further improved. The heat treatment step S4 is preferably carried out in an environment having an oxygen partial pressure (below the oxygen partial pressure in an atmospheric environment) of 2.1 x 10 Å or less. Further, in the present invention, the partial pressure of oxygen is the pressure occupied by oxygen in the heat treatment furnace which has been subjected to the heat treatment step S4 (again, in the present invention, the composition of the atmosphere is nitrogen: oxygen is approximately 4:1). For example, when the film thickness of the alloy film 3 is relatively thin to 3 to 5 nm, the oxygen partial pressure should be heat-treated for a short time of about 1 to 15 minutes in an environment below the oxygen partial pressure in the atmosphere, if the alloy film 3 is 50 nm or more, even if it is heat-treated in the atmosphere for about 1 to 50 minutes, good results can be obtained. Further, when the content of the noble metal element is heat-treated at a high temperature (for example, 500 ° C) in an atomic ratio of about 5 to 25 %, the lower the partial pressure of oxygen, the better the conductivity can be obtained. For the properties, corrosion resistance, etc., it is preferable to appropriately adjust the oxygen partial pressure, temperature, and time by the ratio of the film thickness of the alloy film 3 to the content of the noble metal element. Further, even in the case of a low partial pressure of oxygen, in the vacuum degree which is realistically reachable, when the concentrated phase of the non-precious metal element is exposed on the surface of the alloy coating 3, the oxide film is formed on the surface thereof, so that the alloy coating can be To ensure conductivity and to exert uranium resistance, the partial pressure of oxygen should be 13.33 Pa or less, more preferably 1.33 Pa or less. This heat treatment step S4 can be carried out by using a conventional heat treatment furnace such as an electric furnace or a gas furnace in a vacuum furnace. The fuel cell separator 1 manufactured by the production method of the present invention can be suitably used as a fuel cell because the surface of the metal substrate 2 has an alloy coating 3' which satisfies conductivity and corrosion resistance as in the above-mentioned -21 to 200843180. Metal partition. Next, the fuel cell separator 1 of the present invention produced by the above-described method for producing a metal separator for a fuel cell of the present invention will be described in detail. As shown in Fig. 2 (A) and (B), the metal separator 1 for a fuel cell of the present invention has a structure in which the alloy film 3 for a metal separator of the present invention is formed on the surface of the metal substrate 2, and the metal The substrate 2 is formed as a concave portion for forming a gas flow path 2 1 for flowing a gas on at least a part of the surface. Next, the fuel cell according to the present invention will be described with reference to an appropriate drawing. As shown in Fig. 3, the fuel cell 20 of the present invention has a structure in which a single-cell battery 10 has a structure in which a plurality of cells are stacked, and the single-cell battery 10 is interposed between two carbon cloths 33 and 33. The solid polymer film 32 is housed, and further, the structure of the metal separators 3 1 and 31 for fuel cells of the present invention described above is laminated on the outer side of the carbon cloths 3 3 and 3 3 . The fuel cell 20 is, for example, prepared with a specific number of titanium or titanium alloy metal substrates 2, and the metal substrate 2 of this specific number is formed to have a specific size of a so-called vertical width of 95.2 mm x a width of 95.2 mm x a thickness of 19 mm, and is also on the substrate 2 thereof. The central portion of the surface is formed into a concave portion having a groove width of 0.6 mm and a groove depth of 5 mm by machining, etching, or the like to form a gas flow path 21 having a shape as shown in FIG. Then, the metal substrate 2 forming the concave portion is used to perform the film forming step S3 and the heat treatment step S4, whereby the metal separator 1 for a specific number of fuel cells can be produced. Then, as shown in FIG. 3, the fuel cell-22-200843180 of the specific number to be manufactured is used to form the gas flow path 2 1 with the metal separator 31, for example, two sheets, and the gas flow path 21 is formed to face the gas flow path. a gas diffusion layer composed of a carbon cloth 33 or the like for uniformly diffusing a gas on the film, and a gas diffusion layer between the gas diffusion layer and the other gas diffusion layer The solid polymer film 3 2 coated with a platinum catalyst on the surface is caught to form a single cell 10 . In the same way, a plurality of single-cell batteries 1 are stacked and stacked in a plurality of cells (not shown), and other specific parts are mounted and connected to the fuel cell to provide good corrosion resistance. A fuel cell (solid polymer fuel cell) 20 of the present invention having properties and conductivity. In addition, the solid polymer film 32 used in the fuel cell 20 is not particularly limited as long as it has a function of moving the proton generated in the cathode toward the anode, and can be used, for example, in a sulfhydryl group. A fluorine-based polymer film. The fuel cell 20 produced in this manner introduces a fuel gas (for example, hydrogen having a purity of 99.999%) through a gas flow path to a metal separator 31 for a fuel cell disposed as an anode, and a metal separator for a fuel cell disposed as a cathode. The plate 3 1 introduces air through a gas flow path. At this time, it is preferable that the fuel cell 20 is heated to a temperature of about 80 °C, and the dew point temperature is adjusted to 8 〇 ° C by passing the aforementioned hydrogen gas and air through the heated water. Further, it is preferable that the gas (hydrogen gas) and the air are introduced at a pressure of, for example, 2026 hPa (2 atm). In the fuel cell 20, hydrogen gas is introduced into the anode, and the gas diffusion layer is uniformly supplied to the fixed polymer film 32, and the solid polymer film 32 is reacted by the following formula (1). -23- 200843180 2H + + 2e' (1) In addition, the fuel cell 20 is uniformly supplied to the fixed polymer film 32 by introducing air to the cathode, and the solid film 32 is produced as follows. The reaction of the formula (2). 4H + + 02 + 4e-~>2Η20·_. (2) The reaction of the above formula (1) is produced in the solid polymer film 32, and a voltage of about 1.2 V can theoretically be obtained. Here, the fuel cell 20 of the present invention has the metal separator 1 for a fuel cell as described above, and thus exhibits excellent corrosion resistance and electrical conductivity as compared with a fuel cell using a conventional metal plate. The target material for sputtering (not shown) is used to form the alloy film 3 for a metal separator for a fuel cell, so that at least one noble metal element selected from Au Wan and selected from Ti, Zr, Nb, Hf; The non-noble metal element of at least one of the constituent groups is composed of (the noble metal element/non-precious metal element) of 3 5/65 to 95/5. For small-scale production, a wafer of a non-precious metal element of a precious metal element or a wafer of a target noble metal element of a non-precious metal element is used as a target material for sputtering, and an alloy coating film having a changed composition is formed. However, in this method, the reproducibility of the alloy composition of the film sometimes deteriorates. Therefore, in the metal separator gas expansion high score (2), the atomic ratio of the C Ta atomic ratio of the above-mentioned L Pt is used to bond the target, and the alloy can also be formed into a film - 24 - 200843180 When the film 3 is mass-produced, a large amount of alloy film is formed. Therefore, after the composition is studied, it is preferable to form an alloy target of a desired composition to form an alloy film 3, and the type of the element constituting the alloy sometimes The composition of the alloy target material is deviated from the composition of the alloy film. It is considered that the type of the element is mainly caused by scattering of the collision with the Ar ions and appearing outside the metal substrate 2 during the sputtering, in which each atom moves from the surface of the target material toward the metal substrate 2. However, it is difficult for the noble metal element and the non-noble metal element selected in the present invention to cause such scattering, and the alloy film 3 having the same composition as the target material can be obtained. The target material for sputtering of the present invention can be produced by a powder metallurgy method or a melting method, but when the combined melting point or specific gravity of the precious metal element and the non-precious metal element is greatly different, or it is difficult to solidify each other It is difficult to produce the combination of the elements by the melt method, and therefore it is preferable to carry out the production by the powder metallurgy method. At this time, it is possible to "raw material mixing - mold filling - mold degassing -> HIP (hot hydrostatic pressing) sintering - > stripping θ forging θ rolling θ machining '^ joining the stacked sheets' The process is manufactured. When such a target material for sputtering is used, an alloy film 3 having a stable film composition can be formed, and a metal separator 3 1 and a fuel cell 20 of a fuel cell of stable performance can be provided. [Embodiment] The alloy film for a metal separator for a fuel cell of the present invention, the method for producing the same, the metal separator, and the fuel cell, satisfy the embodiment of the present invention and do not satisfy the present invention. Comparative example of the requirements <Examples 1 to 8 and Comparative Examples 1 to 7 > A titanium alloy (20 x 50 x 0 · 15 mm, arithmetic mean roughness (Ra) = 15 nm) composed of one of the types specified by JIS Η 4600 was used as a propane wave. After washing, it is mounted on the substrate table in the chamber. Then, in the case of a target for alloy formation, a non-noble metal wafer attached to a target of a noble metal element or a target of a non-precious metal element is attached to a precious metal element (using either a noble metal element or a non-precious metal element) The target (which is expressed as "the ratio of precious metal element/non-precious metal element" in Tables 1 to 5) (atomic ratio) is attached to the chamber, and the chamber is evacuated to 0.00133 Pa or less. vacuum. Here, the surface roughness of the substrate is measured using the surface roughness measuring device Dektak 6M), and is selected from the thickness curve obtained by the measurement! Ra is calculated from the range of jczm. Next, Ar gas was introduced into the chamber, and the inside of the chamber was adjusted to 0.266 Pa. Thereafter, RF (frequency) of 100 W, 13·5 6 输出 was applied to the target to generate argon plasma for sputtering, and an alloy film of a desired composition was formed on one surface. Further flipping the substrate The same method is used to form the film. Here, 'change the metal element species used for the target or wafer to change the combination of precious metal elements and non-precious metal elements in the gold film, and the description of the substrate ketone super-film element wafer ratio electrode (p 20 pressure) Frequency substrate, change the number of wafers adhered to the target by the change of -26- 200843180, to change the content ratio of precious metal elements and non-precious metal elements in the alloy film, and change the film formation time to control the film thickness to form The alloy film of the alloy film of Table 1. Then, the substrate on which the alloy film was formed was heat-treated at 50,000 ° C for 5 minutes in a vacuum atmosphere of 〇〇 665 Pa to obtain a test plate. The ratio of the ratio of the noble metal element to the non-noble metal element in the film (atomic ratio), the film thickness of the alloy film, and the contact resistance before heat treatment. Moreover, in terms of the corrosion resistance index in an acidic environment, the sulfuric acid dipping is measured. Contact resistance. The ratio of the content of precious metal elements to non-precious metal elements is determined by the precious metal elements in the alloy film of the obtained test plate. The ratio of the content to the non-noble metal element (atomic ratio) is determined by ICP (Inductively C 〇 1 ed P1 asma) luminescence analysis method. Here, an acid solution which dissolves the alloy film together with the substrate is used. On the other hand, the test plate was dissolved, and the concentration of the noble metal element and the non-precious metal element in the obtained solution was measured and normalized to 100% to calculate the content ratio (atomic ratio) of the noble metal element and the non-precious metal element in the alloy film. Further, when the non-precious metal element is Ti, the alloy film is formed on the Si wafer substrate and measured. The contact resistance before and after the heat treatment is measured on the surface of the metal substrate after the alloy film is formed (before heat treatment), and the alloy film is formed. Thereafter, the test plate for heat treatment (after heat treatment of -27-200843180) was used, and the contact resistance before and after the heat treatment was measured using the contact resistance measuring device shown in Fig. 4. That is, the two sides of the test plate 4 were made into two pieces. The carbon cloths 42, 42 are caught, and further, two copper electrodes 43, 43 having a contact area of 1 cm 2 are clamped on the outer side thereof to have a load of 98 N (10 Kgf). Pressurization, a current of 1 A is applied using a direct current power source 44, and a voltage applied between the carbon cloths 4 2 and 4 2 is measured by a voltmeter 4 5 to determine a contact resistance. Contact resistance after immersion in a sulfuric acid aqueous solution is tested. The plate 4 1 is concealed and partially immersed in an aqueous solution of 8 5 C of sulfuric acid (1 〇mm ο 1 /liter) for 500 hours, and then taken out from the aqueous sulfuric acid solution and washed. After the drying, the masking material was removed, and the contact resistance was measured in the same manner as described above. The contact resistance after the immersion of the sulfuric acid aqueous solution was 15 m Ω · cm 2 or less was acceptable. The ratio of the ratio of the noble metal element to the non-precious metal element (atomic ratio) in the alloy coating film of each test plate, the film thickness of the alloy film, the contact resistance before and after the heat treatment, and the contact resistance after immersion in the sulfuric acid aqueous solution are shown in Table 1. in. -28- 200843180 [Table 1] Alloy Luo contact resistance (πιΩ · cm2) Precious metal species: Non-precious metal species Precious metal element/non-precious metal element content ratio (atomic ratio) Film thickness (nm) Example after immersion in sulfuric acid aqueous solution after heat treatment before heat treatment 1 Au Ta 75/25 3 4.2 3.0 5.1 Example 2 Au Ta 65/35 10 5.2 3.1 6.4 Example 3 Au Ta 40/60 30 3.3 3.3 3.9 Example 4 An Nb 55/45 10 6.0 4.2 6.9 Example 5 Au Nb 85/15 5 3.8 2.9 4.1 Example 6 Pt Ta 50/50 50 4.3 4.3 4.7 Example 7 Pt Ta 90/10 5 4.8 3.8 5.2 Example 8 Pt Nb 40/60 20 3.5 3.6 5.1 Comparative Example 1 Au Ta 30 /70 10 4.3 7.2 220 Comparative Example 2 Au Ta 60/40 1 7.2 26.7 221.5 Comparative Example 3 Au Ta 98/2 5 4.0 2.8 Ϊ9.8 Comparative Example 4 Pt Nb 75/25 1 10.2 77.5 253.0 Comparative Example 5 Pt Nb 98 /2 10 4.1 2.9 51.5 Comparative Example 6 Ag Nb 70/30 10 6.5 5.0 99.3 Comparative Example 7 Ag Ta 55/45 10 10.0 9.6 125.6

在比較例3與比較例5之試驗板中係貴金屬之含有比 率多。因此’可知熱處理後之接觸電阻低，但硫酸水溶液 浸漬後之接觸電阻會增加，在酸性環境中之耐蝕性差。認 爲此係於硫酸水溶液之浸漬中引起合金被膜之凝集，於基 板與合金膜之界面形成厚的氧化被膜。 在比較例2與4之試驗板中熱處理前係接觸電阻爲比 較低的値，但合金被膜之膜厚薄，故藉熱處理氧化過度進 行而可看到接觸電阻之增加。又，在比較例2與4之試驗 板係於硫酸水溶液的浸漬後可看到接觸電阻之增加。認爲 -29- 200843180 因合金被膜之膜厚薄，故針孔等基板露出之部份很多，於 基板與合金膜之界面形成厚的氧化被膜。認爲在比較例6 與7之試驗板中Ag係於85°C、lOmmol/升之硫酸水溶液 中氧化或一部份溶解，產生接觸電阻之增加者。 對此，於實施例1〜8的試驗板中係受合金被膜中之貴 金屬之含有比率與膜厚而性能改變，但顯示良好的導電性 與耐蝕性。 〈實施例9〜16、比較例8〜12&gt; 於丙酮中洗淨由SUS304所構成之基板（ 20x50xlmm 、Ra=12nm)後，依與實施例1同樣之濺鍍方法而形成具 有表2所示之貴金屬元素的含有比率與膜厚之合金被膜。 然後，使形成合金被膜之基板於〇.〇〇665Pa之真空環境中 以5 00 °C熱處理5分鐘而得到試驗板。 有關所得到之試驗板，依與實施例1同樣之方法而測 φ 定合金被膜中之貴金屬元素與非貴金屬元素的含有比率、 與膜厚之熱處理前後的接觸電阻及硫酸水溶液浸漬後之接 觸電阻。 有關各試驗板，將合金被膜中之貴金屬元素與非貴金 屬元素的含有比率、熱處理前後的接觸電阻及硫酸水溶液 浸漬後之接觸電阻的測定結果表示於表 2。 -30- 200843180 〔表2〕 合金被膜 接觸電阻(ιηΩ · cm2) 貴金屬種 非貴金屬種 貴金屬元素/非貴金 屬元素之含有比率 (原子比） 膜厚 (nm) 熱處理前 熱處理後 硫酸水溶 液浸漬後 實施例9 An Ti 45/55 10 6.9 5.0 8.7 實施例10 Au Zr 40/60 25 6.0 6.2 6.9 實施例11 Au Zr 72/28 5 6.9 5.5 8.2 實施例Π Au Hf 90/10 5 6.5 4.0 12.5 實施例13 Au Hf 46/54 40 4.2 4.0 9.0 實施例14 Pt Ti 70/30 20 5.0 3.9 6.3 實施例15 Pt Zr 55/45 10 6.9 4.5 6.5 實施例16 Pt Nb 85/15 5 5.2 4.2 7.5 比較例8 Au Ta 25/75 1 20.1 65.2 132.1 比較例9 Au Ti 40/60 1 7.6 45.6 105.6 比較例10 Au Zr 80/20 1 7.0 32.6 88.8 比較例11 Pt Nb 98/2 1 7.2 33.5 105.0 比較例12 Pt Nb 30/70 1 8.2 48.6 112.2In the test plates of Comparative Example 3 and Comparative Example 5, the content ratio of the noble metal was large. Therefore, it is understood that the contact resistance after the heat treatment is low, but the contact resistance after immersion in the sulfuric acid aqueous solution is increased, and the corrosion resistance in an acidic environment is poor. It is considered that the alloy film is agglomerated in the immersion of the aqueous sulfuric acid solution, and a thick oxide film is formed at the interface between the substrate and the alloy film. In the test plates of Comparative Examples 2 and 4, the contact resistance was lower than that of the alloy before the heat treatment, but the film thickness of the alloy film was thin, so that the contact resistance was increased by excessive heat treatment by heat treatment. Further, in the test sheets of Comparative Examples 2 and 4, an increase in contact resistance was observed after immersion in an aqueous sulfuric acid solution. It is considered that -29-200843180 has a thin film thickness of the alloy film, so that a substrate such as a pinhole is exposed, and a thick oxide film is formed at the interface between the substrate and the alloy film. It is considered that in the test plates of Comparative Examples 6 and 7, the Ag system was oxidized or partially dissolved in an aqueous solution of sulfuric acid at 85 ° C, 10 mmol / liter, resulting in an increase in contact resistance. On the other hand, in the test plates of Examples 1 to 8, the content ratio of the noble metal in the alloy film was changed to the film thickness, and the performance was changed, but good conductivity and corrosion resistance were exhibited. <Examples 9 to 16 and Comparative Examples 8 to 12> After the substrate (20×50×1 mm, Ra=12 nm) composed of SUS304 was washed with acetone, the same sputtering method as in Example 1 was carried out, and it was shown in Table 2. An alloy coating film having a ratio of a noble metal element to a film thickness. Then, the substrate on which the alloy film was formed was heat-treated at 500 ° C for 5 minutes in a vacuum atmosphere of 〇 〇〇 665 Pa to obtain a test plate. With respect to the obtained test plate, the content ratio of the noble metal element to the non-precious metal element in the alloy film was measured in the same manner as in Example 1, the contact resistance before and after the heat treatment with the film thickness, and the contact resistance after the immersion in the sulfuric acid aqueous solution. . The measurement results of the contact resistance of the noble metal element and the non-precious metal element in the alloy coating film, the contact resistance before and after the heat treatment, and the contact resistance after the sulfuric acid aqueous solution were impregnated in each test plate are shown in Table 2. -30- 200843180 [Table 2] Alloy film contact resistance (ιηΩ · cm2) Precious metal species Non-precious metal species Precious metal element/non-precious metal element content ratio (atomic ratio) Film thickness (nm) Example after immersion in sulfuric acid aqueous solution after heat treatment before heat treatment 9 An Ti 45/55 10 6.9 5.0 8.7 Example 10 Au Zr 40/60 25 6.0 6.2 6.9 Example 11 Au Zr 72/28 5 6.9 5.5 8.2 Example Π Au Hf 90/10 5 6.5 4.0 12.5 Example 13 Au Hf 46/54 40 4.2 4.0 9.0 Example 14 Pt Ti 70/30 20 5.0 3.9 6.3 Example 15 Pt Zr 55/45 10 6.9 4.5 6.5 Example 16 Pt Nb 85/15 5 5.2 4.2 7.5 Comparative Example 8 Au Ta 25 /75 1 20.1 65.2 132.1 Comparative Example 9 Au Ti 40/60 1 7.6 45.6 105.6 Comparative Example 10 Au Zr 80/20 1 7.0 32.6 88.8 Comparative Example 11 Pt Nb 98/2 1 7.2 33.5 105.0 Comparative Example 12 Pt Nb 30/70 1 8.2 48.6 112.2

在比較例8、9、1 0、1 1及1 2之試驗板中熱處理前係 接觸電阻比較低，但合金被膜之膜厚薄，熱處理後可看到 接觸電阻之增加。又，此等之比較例8、9、1 0、1 1及1 2 之試驗板係於硫酸水溶液的浸漬後可看到接觸電阻之增加 。認爲此係因合金被膜之膜厚薄，故針孔等基板露出之部 份很多，於基板與合金膜之界面形成厚的氧化被膜。對此 ，於實施例9〜16的試驗板中係受合金被膜之膜厚爲2nm 以上，依照其合金被膜中之貴金屬的含有比率與合金被膜 之膜厚而性能變化，但任一者均顯示良好的導電性與耐蝕 性。 -31 - 200843180 〈實施例17〜20、比較例13、比較例14 &gt; 於丙酮中超音波洗淨由JIS Η 4600所規定之i種的純 鈦所構成之鈦製基板（20x50 x0.15mm、Ra= 15 nm)後，依 與實施例1同樣之濺鍍方法而形成具有表3所示之貴金屬 元素的含有比率與膜厚之合金被膜。然後，其後，以表3 所示之各種熱處理條件進行熱處理，得到試驗板。此處， g 氧分壓係使熱處理爐內真空排氣至0.00133Pa，加熱至特 定之溫度後，如成爲表3所示之氧分壓，一邊爐內排氣， 一邊導入氧而調整。依與實施例1同樣之方法而測定各別 之試驗板的合金被膜之貴金屬元素的含有比率、熱處理前 後及硫酸水溶液浸漬後之接觸電阻。 將各試驗板的合金被膜之貴金屬元素與非貴金屬元素 的含有比率及膜厚、熱處理前後的接觸電阻及硫酸水溶液 浸漬後之接觸電阻的測定結果表示於表3。 -32- 200843180 〔表3〕In the test plates of Comparative Examples 8, 9, 10, 1 and 12, the contact resistance was relatively low before the heat treatment, but the film thickness of the alloy film was thin, and the increase in contact resistance was observed after the heat treatment. Further, in the test plates of Comparative Examples 8, 9, 10, 1 1 and 1 2, an increase in contact resistance was observed after immersion in an aqueous sulfuric acid solution. It is considered that since the film thickness of the alloy film is small, a portion such as a pinhole is exposed, and a thick oxide film is formed at the interface between the substrate and the alloy film. On the other hand, in the test sheets of Examples 9 to 16, the film thickness of the alloy coating film was 2 nm or more, and the performance was changed depending on the content ratio of the noble metal in the alloy coating film and the film thickness of the alloy coating film, but either of them was displayed. Good electrical conductivity and corrosion resistance. -31 - 200843180 <Examples 17 to 20, Comparative Example 13, and Comparative Example 14 &gt; A titanium substrate (20 x 50 x 0.15 mm) composed of pure titanium of the type I specified in JIS Η 4600 was ultrasonically washed in acetone. After Ra = 15 nm), an alloy film having a content ratio and a film thickness of the noble metal element shown in Table 3 was formed by the same sputtering method as in Example 1. Then, heat treatment was performed under various heat treatment conditions shown in Table 3 to obtain a test plate. Here, the g oxygen partial pressure system evacuates the inside of the heat treatment furnace to 0.00133 Pa, and after heating to a specific temperature, the oxygen partial pressure shown in Table 3 is used, and the inside of the furnace is exhausted, and oxygen is introduced and adjusted. The content ratio of the noble metal element of the alloy coating film of each test plate, and the contact resistance after the heat treatment and the immersion of the sulfuric acid aqueous solution were measured in the same manner as in Example 1. Table 3 shows the measurement results of the contact ratio of the noble metal element and the non-precious metal element in the alloy coating film of each test plate, the film thickness, the contact resistance before and after the heat treatment, and the contact resistance after immersion in the sulfuric acid aqueous solution. -32- 200843180 [Table 3]

合金被膜 熱處理條 接觸1 | 阻(ιηΩ · cm2) 貴金 屬種 非貴金 屬種 貴金屬元素/ 非貴金屬元素 之含有比率 (原子比） 膜厚 (ran) 酸素分 壓(Pa) 熱處理 urn (°c ) 熱處理 時間 (分） 熱處理 前 熱處理 後 硫酸水 溶液浸 漬後 實施例 17 Au Ta 50/50 10 0.133 500 30 5.0 5.4 7.6 實施例 18 Αυ Nb 80/20 10 1.33 400 45 3.8 3.2 6.6 實施例 19 Pt Ta 40/60 5 0.0133 300 30 7.6 6.5 10.5 實施例 20 Pt Zr 75/25 10 13.3 600 5 6.0 4.5 5.8 比較例 13 Au Ta 98/2 5 0.133 820 10 4.5 22.7 25.5 比較例 14 Pt Nb 33/67 10 133 850 10 6.1 32.5 38.2 在比較例1 3之試驗板中係熱處理後可看到接觸電阻 之增加。認爲因熱處理溫度太高，故合金被膜會凝集，於 基板表面形成厚的氧化被膜。 在比較例1 4之試驗板中係熱處理後可看到接觸電阻 之增加。認爲合金被膜係不凝集，但熱處理溫度太高，故 於合金被膜表面形成厚氧化被膜，熱處理後之接觸電阻明 顯變高。然而，在實施例17〜20之試驗板中，以800°C以 下之溫度進行熱處理，故，依照合金被膜中之貴金屬的含 有比率與合金被膜之膜厚而性能變化，但任一者均顯示良 好的導電性與耐蝕性。 〈實施例21〜36、比較例15〜18 &gt; 於丙酮中超音波洗淨由JIS Η 4600所規定之1種的純 -33- 200843180 鈦所構成之鈦製基板（20x50x0.15mm、Ra=15nm)後’依 與實施例1同樣之濺鍍方法而形成合金被膜。又，任一者 均合金被膜形成用標靶的貴金屬元素係使用Au，非貴金 屬元素係使用Ta。又，調整成膜時間而膜厚成爲2 0 nm， 其後，以表4所示之各種熱處理條件（以熱處理環境（Pa )、熱處理溫度（°C ))進行熱處理，得到試驗板。熱處 理係以各溫度保持5分鐘進行。 _ 依與實施例1同樣之方法而測定各別之試驗板的合金 被膜之貴金屬元素的含有比率（An/Ta )(原子比）、熱 處理前後及硫酸水溶液浸漬後之接觸電阻（m Q · em2丨。 將各別試驗板的合金被膜之貴金屬元素/非貴金屬亓； 素的含有比率、熱處理前後的接觸電阻及硫酸水溶液浸漬 後之接觸電阻的測定結果與熱處理條件一起表示於表4中 〇 -34 - 200843180 〔表4〕Alloy film heat treatment strip contact 1 | resistance (ιηΩ · cm2) precious metal non-precious metal species precious metal element / non-precious metal element content ratio (atomic ratio) film thickness (ran) acid partial pressure (Pa) heat treatment urn (°c) heat treatment time (Minute) Example 17 after the heat treatment of the sulfuric acid aqueous solution after heat treatment. Au Ta 50/50 10 0.133 500 30 5.0 5.4 7.6 Example 18 Αυ Nb 80/20 10 1.33 400 45 3.8 3.2 6.6 Example 19 Pt Ta 40/60 5 0.0133 300 30 7.6 6.5 10.5 Example 20 Pt Zr 75/25 10 13.3 600 5 6.0 4.5 5.8 Comparative Example 13 Au Ta 98/2 5 0.133 820 10 4.5 22.7 25.5 Comparative Example 14 Pt Nb 33/67 10 133 850 10 6.1 32.5 38.2 An increase in contact resistance was observed after heat treatment in the test plate of Comparative Example 1 3. It is considered that since the heat treatment temperature is too high, the alloy film aggregates to form a thick oxide film on the surface of the substrate. An increase in contact resistance was observed after heat treatment in the test plate of Comparative Example 14. It is considered that the alloy film is not aggregated, but the heat treatment temperature is too high, so that a thick oxide film is formed on the surface of the alloy film, and the contact resistance after heat treatment is remarkably high. However, in the test plates of Examples 17 to 20, the heat treatment was performed at a temperature of 800 ° C or lower, and the performance was changed depending on the content ratio of the noble metal in the alloy film and the film thickness of the alloy film, but either of them was displayed. Good electrical conductivity and corrosion resistance. <Examples 21 to 36, and Comparative Examples 15 to 18 &gt; A titanium substrate made of pure-33-200843180 titanium of one type defined by JIS Η 4600 was ultrasonically washed in acetone (20 x 50 x 0.15 mm, Ra = 15 nm). After that, an alloy film was formed in the same manner as in the sputtering method of Example 1. Further, in any of the noble metal elements of the alloy film forming target, Au is used, and in the non-precious metal element, Ta is used. Further, the film formation time was adjusted to a thickness of 20 nm, and thereafter, heat treatment was performed under various heat treatment conditions (heat treatment environment (Pa), heat treatment temperature (°C)) shown in Table 4 to obtain a test plate. The heat treatment was carried out for 5 minutes at each temperature. _ The content ratio (An/Ta) (atomic ratio) of the noble metal element of the alloy coating film of each test plate was measured in the same manner as in Example 1, and the contact resistance after the heat treatment and the immersion of the sulfuric acid aqueous solution (m Q · em2)贵. The precious metal element/non-precious metal bismuth of the alloy coating film of each test plate; the content ratio of the element, the contact resistance before and after the heat treatment, and the contact resistance after immersion in the sulfuric acid aqueous solution are shown in Table 4 together with the heat treatment conditions. 34 - 200843180 [Table 4]

貴金屬兀素/非 貴金屬元素之 含有比率 (Au/Ta) (原子比) 熱處理條件 接觸電阻(πιΩ · cm2) 熱處理環境 (Pa) 熱處理溫度 (°C ) 熱處理前 熱處理後 硫酸水溶 液浸瀆後 實施例21 80/20 無熱處理 無熱處理 3.9 3.9 9.3 實施例22 37/63 無熱處理 無熱處理 3.5 3.5 5.1 實施例23 80/20 大氣壓 200 3.9 3.8 3.9 實施例24 37/63 大氣壓 200 3.5 32 4.1 實施例25 80/20 大氣壓 400 3.9 3.3 4.5 實施例26 37/63 大氣壓 400 3.5 5.1 6.3 實施例27 80/20 大氣壓 500 3.9 4.7 7.2 實施例28 80/20 0.00665 300 3.9 2.5 4.5 實施例29 37/63 0.00665 300 3.5 2.4 3.9 實施例30 95/5 0.00665 400 3.2 2.6 5.2 實施例31 80/20 0.00665 400 3.9 3.6 4.6 實施例32 37/63 0.00665 400 3.5 3.2 4.0 實施例33 80/20 0.00665 500 3.9 3.6' 4.8 實施例134 37/63 0.00665 500 3.5 3.6 5.0 實施例35 80/20 0.00665 600 3.9 5.0 5.6 實施例36 37/63 0.00665 600 3.5 3.9 5.1 比較例15 30/70 無熱處理 無熱處理 4.3 4.3 52.4 比較例16 30/70 大氣壓 200 4.3 4.0 18.3 比較例17 30/70 大氣壓 400 4.3 15.0 66.3 比較例18 30/70 0.00665 400 4.3 5.8 165.0 比較例1 5之試驗板，成膜後之接觸電阻係非貴金屬 元素之含有比率低於此者幾乎不變，但非貴金屬元素之含 有比率高，故硫酸水溶液浸漬後接觸電阻會增加。 比較例1 6之試驗板，係非貴金屬元素之含有比率高 的比較例1 5之試驗板以大氣壓條件下、比較低的熱處理 條件進行熱處理者。比較例16之試驗板係超過硫酸水溶 液浸漬後之接觸電阻較比較例1 5之試驗板低者之1 5m Ω -35- 200843180 比較例1 7之試驗板，係非貴金屬元素之含有比率高 的比較例1 5之試驗板以大氣壓條件下、比較低的熱處理 條件進行熱處理者。比較例1 7之試驗板係熱處理後接觸 電阻會增加。又，硫酸水溶液浸漬後之接觸電阻亦增加。 比較例1 8之試驗板係使比較例1 5之試驗板於真空中 (0.006 65 Pa)進行熱處理者。比較例1 8之試驗板係熱處 理後之接觸電阻爲15 ηιΩ · cm2以下，但硫酸水溶液浸漬 後接觸電阻增大許多。 對此，於實施例21〜36的試驗板係受合金被膜中之貴 金屬的含有比率與熱處理條件而性能變化，但顯示良好的 導電性與耐蝕性。 &lt;實施例3 7、實施例3 8、比較例1 9 &gt; 於丙酮中超音波洗淨由已鏡面硏磨之JIS Η 4600所規 定之1種的純鈦所構成之鈦製基板（ 20 x 50 x 0.1 5mm、 R a == 3 n m )後，依與實施例1同樣之 '濺鍍方法而形成合金 被膜。又，合金被膜形成用標靶的貴金屬元素係使用Au ，非貴金屬元素係使用Ta。又，調整成膜時間而膜厚成 爲20nm。其後，以表5所示之各種之熱處理條件（以熱 處理環境（Pa )、熱處理溫度（°C ))進行熱處理，得到 試驗板。熱處理係以各溫度保持5分鐘進行。 依與實施例1同樣之方法而測定各別之試驗板的合金 被膜之貴金屬元素/非貴金屬元素的含有比率（Aii/Ta )( -36 - 200843180 原子比）、熱處理前後及硫酸水溶液浸漬後之接觸電阻（ m Ω · cm2 )。又硫酸水溶液浸漬後之接觸電阻係使各別之 試驗板浸漬於80°C之硫酸水溶液（Imol/升）浸漬100小 時而測定接觸電阻。 將各別試驗板的合金被膜之貴金屬元素/非貴金屬元 素的含有比率、熱處理後的接觸電阻及硫酸水溶液浸漬後 之接觸電阻的測定結果表示於表5中。Content ratio of noble metal halogen/non-precious metal element (Au/Ta) (atomic ratio) Heat treatment condition Contact resistance (πιΩ · cm2) Heat treatment environment (Pa) Heat treatment temperature (°C) Example after immersion in sulfuric acid aqueous solution after heat treatment before heat treatment 21 80/20 No heat treatment without heat treatment 3.9 3.9 9.3 Example 22 37/63 No heat treatment without heat treatment 3.5 3.5 5.1 Example 23 80/20 Atmospheric pressure 200 3.9 3.8 3.9 Example 24 37/63 Atmospheric pressure 200 3.5 32 4.1 Example 25 80 /20 Atmospheric pressure 400 3.9 3.3 4.5 Example 26 37/63 Atmospheric pressure 400 3.5 5.1 6.3 Example 27 80/20 Atmospheric pressure 500 3.9 4.7 7.2 Example 28 80/20 0.00665 300 3.9 2.5 4.5 Example 29 37/63 0.00665 300 3.5 2.4 3.9 Example 30 95/5 0.00665 400 3.2 2.6 5.2 Example 31 80/20 0.00665 400 3.9 3.6 4.6 Example 32 37/63 0.00665 400 3.5 3.2 4.0 Example 33 80/20 0.00665 500 3.9 3.6' 4.8 Example 134 37 /63 0.00665 500 3.5 3.6 5.0 Example 35 80/20 0.00665 600 3.9 5.0 5.6 Example 36 37/63 0.00665 600 3.5 3.9 5.1 Comparative Example 15 30/70 No heat treatment without heat treatment 4.3 4.3 52.4 Comparative Example 16 30/70 Atmospheric pressure 200 4.3 4.0 18.3 Comparative Example 17 30/70 Atmospheric pressure 400 4.3 15.0 66.3 Comparative Example 18 30/70 0.00665 400 4.3 5.8 165.0 Comparative Example 1 Test plate of 5, contact resistance after film formation is non-precious metal The content ratio of the element is almost unchanged, but the content ratio of the non-precious metal element is high, so the contact resistance increases after the immersion of the sulfuric acid aqueous solution. In the test plate of Comparative Example 1, the test plate of Comparative Example 15 having a high content ratio of non-precious metal elements was subjected to heat treatment under atmospheric pressure conditions and relatively low heat treatment conditions. The contact resistance of the test plate of Comparative Example 16 after the immersion in the sulfuric acid aqueous solution was lower than that of the test plate of Comparative Example 15. 5 m Ω -35 - 200843180 The test plate of Comparative Example 1 7 was a high content ratio of non-precious metal elements. The test plate of Comparative Example 1 was subjected to heat treatment under atmospheric pressure conditions and relatively low heat treatment conditions. The contact resistance of the test plate of Comparative Example 1 7 was increased after heat treatment. Further, the contact resistance after the immersion of the sulfuric acid aqueous solution also increases. The test plate of Comparative Example 1 was subjected to heat treatment in a test plate of Comparative Example 15 in a vacuum (0.006 65 Pa). The contact resistance of the test plate of Comparative Example 1 was 15 ηιΩ · cm2 or less after heat treatment, but the contact resistance increased a lot after immersion in an aqueous sulfuric acid solution. On the other hand, the test sheets of Examples 21 to 36 were changed in the content ratio of the noble metal in the alloy film and the heat treatment conditions, but showed good electrical conductivity and corrosion resistance. &lt;Example 3, Example 3, Comparative Example 1 9 &gt; Ultrasonic cleaning of a titanium substrate (20 x) composed of one type of pure titanium specified by JIS Η 4600 which has been mirror-honed in acetone After 50 x 0.1 5 mm and R a == 3 nm), an alloy film was formed by the same sputtering method as in Example 1. Further, Au is used as the noble metal element for the alloy film formation target, and Ta is used as the non-precious metal element. Further, the film formation time was adjusted to have a film thickness of 20 nm. Thereafter, heat treatment was carried out under various heat treatment conditions (heat treatment environment (Pa), heat treatment temperature (°C)) shown in Table 5 to obtain a test plate. The heat treatment was carried out at each temperature for 5 minutes. The content ratio of the noble metal element/non-precious metal element (Aii/Ta) (-36 - 200843180 atomic ratio) of the alloy coating film of each test plate was measured in the same manner as in Example 1, before and after the heat treatment and the immersion in the sulfuric acid aqueous solution. Contact resistance ( m Ω · cm2 ). Further, the contact resistance after the immersion in the sulfuric acid aqueous solution was such that the respective test plates were immersed in a sulfuric acid aqueous solution (Imol/liter) at 80 ° C for 100 hours to measure the contact resistance. The measurement results of the contact ratio of the noble metal element/non-precious metal element of the alloy coating film of each test plate, the contact resistance after heat treatment, and the contact resistance after immersion in the sulfuric acid aqueous solution are shown in Table 5.

〔表5〕 貴金屬元素/非 貴金屬元素之 含有比率 (Au/Ta) (原子比） 熱處理1 牛 接觸電阻(πιΩ · cm2) 熱處理環境 (Pa) 熱處理溫度 (°C ) 熱處理前 熱處理後 硫酸水溶 液浸漬後 比較例19 100/0 無熱處理 無熱處理 1.3 1.3 不能測定 實施例37 37/63 無熱處理 無熱處理 1.1 1.1 9.5 實施例38 37/63 0.00665 400 1.1 0.9 9.0 比較例1 9之試驗板係於硫酸水溶液之浸漬試驗後， 鈦基板會溶解，故無法測定接觸電阻。認爲純Au膜會凝 集、剝離，鈦基板露出，溶解者。 然而，實施例37、實施例38之試驗板係藉使基板表 面平滑化，以防止合金被膜中之針孔形成，合金被膜具有 適當之含有比率而使Au與Ta合金化，故即使在硫酸水溶 液浸漬中，亦無損與金屬基板之密著性，而合金被膜不凝 集，又，具有合金被膜優之耐蝕性，故可得到良好的結果 -37- 200843180 〈實施例3 9 &gt; 本發明之金屬隔板組入於燃料電池，以進行發電試驗 〇 金屬隔板係以如下之順序製作。 首先，如圖2(A)所示般，對由鈦板（95·2χ95·2χ 19mm )所構成之金屬基板2的表面中央部以機械加工形 成溝寬0.6mm、溝深0.5mm之氣體流路21。氣體流路21 係於其兩端具有用以導入氫氣或空氣之氣體導入口 22。 當合金被膜之成膜時係製造Au-Ta合金標靶，使用其 而成膜。混合Au與Ta之粉末以使Au組成成爲60原子％ 而依模塡充、模脫氣、HIP、脫模、鍛造、壓延、及機械 加工之順序而進行成形，製造外徑152.4mm ( 6英吋）、 厚5 mm之圓盤型的濺鍍標靶。 然後，於形成氣體流路21之金屬基板2的面上，使 用上述An - Ta濺鍍標靶，而依與實施例1相同之成膜條 件而以被膜厚成爲20mm之方式形成由Au與Ta所構成之 合金被膜。又，使用同濺鍍標靶之條件於純鈦基板上成膜 者，藉ICP發光分析法測定合金被膜中之Au組成之結果 ，確認出與標靶組成約相同的6 1原子％。 然後，使形成由Au與Ta所構成之合金被膜的金屬基 板2，於0.00665Pa的真空環境中以500°C熱處理5分鐘 而製造金屬隔板。 繼而，如圖3所示般，使金屬隔板3 1、3 1組入於 Electrochem公司製之市售的燃料電池（EFC-05-01SP) -38- 200843180 20的單節電池10。在圖3所示之燃料電池中，32係固體 高分子膜，33係碳布。 然後，使用99.999%之氫氣作爲陽極側燃料氣體，使 用空氣作爲陰極側氣體而進行發電試驗。此時，燃料電池 係使全體加熱保溫至80°C，使氫氣及空氣藉通入被加溫之 水中以調整露點溫度至80°C，而以2026hPa ( 2氣壓）之 壓力導入於燃料電池。 接著，使用電池性能測定用系統（Scribner公司製 890CL )，使流入於隔板之電流作爲3 00mA/cm2而發電 1 00小時以測定電壓及輸出之變化。 其結果，鈦基板之隔板的發電初期之電壓及發電1 00 小時後之電壓係均爲0.61 V，看不出電壓之變化。 又，就比較對象而言，取代鈦基板之隔板，而配置自 以往所使用之石墨隔板（Electrochem公司製，FC05 - MP )而製作燃料電池，以與前述相同之條件進行發電試驗。 其結果，發電初期之電壓及發電100小時後之電壓係 均爲0.61V，成爲與鈦基板之隔板相同的結果。 從以上之結果，可知依本發明之燃料電池用隔板的製 造方法所製造之隔板係即使爲金屬製之隔板，亦顯示與石 墨隔板同等之性能。 參照特定之態樣而詳細說明本發明，但不超出本發明 之精神與範圍，可做各種變更及修正係熟悉此技藝者很明 白的。 又，本申請案等係依據2006年12月21日所申請之 -39- 200843180 日本特許申請案（特願2006-344895 )及2007年9月21 日所申請之日本特許申請案（特願2007-2459 1 7 )，其全 體藉引用來援用。 又此處所引用之全部的參照係全體被摘入。 產業上之利用可能性 若依本發明，可提供一種係耐蝕性優，且接觸電阻低 ，即使在腐蝕環境中亦可經長期間維持其低的接觸電阻， 進一步生產性優之燃料電池之金屬隔板用合金被膜、其製 造方法及濺鍍用標靶材料、以及金屬隔板及燃料電池。 【圖式簡單說明】 圖1係說明本發明之燃料電池用金屬隔板的製造方法 之步驟的流程圖。 圖2 ( A )係本發明之燃料電池用金屬隔板的平面圖 ’ （B )係燃料電池用金屬隔板之一部份擴大截面圖。 圖3係說明使用本發明之燃料電池用金屬隔板的燃料 電池之構成的分解剖面圖。 圖4係說明接觸電阻之測定方法的圖。 【主要元件符號說明】 S 1 :形成步驟 52 :設置步驟 53 :成膜步驟 -40- 200843180 參 :熱處理步驟 3 1 :金屬隔板 金屬基板 合金被膜 :單節電池 :燃料電池 :氣體流路 :氣體導入口 :固體高分子膜 :碳布 :試驗板 :碳布 :銅電極 :直流電流電源 :電壓計 -41[Table 5] Content ratio of precious metal element/non-precious metal element (Au/Ta) (atomic ratio) Heat treatment 1 Cattle contact resistance (πιΩ · cm2) Heat treatment environment (Pa) Heat treatment temperature (°C) Immersion of sulfuric acid aqueous solution after heat treatment before heat treatment Comparative Example 19 100/0 No heat treatment without heat treatment 1.3 1.3 Cannot be measured Example 37 37/63 No heat treatment without heat treatment 1.1 1.1 9.5 Example 38 37/63 0.00665 400 1.1 0.9 9.0 Comparative Example 1 The test plate of 9 is in an aqueous solution of sulfuric acid After the immersion test, the titanium substrate was dissolved, so the contact resistance could not be measured. It is considered that the pure Au film is aggregated and peeled off, and the titanium substrate is exposed and dissolved. However, in the test plates of Examples 37 and 38, the surface of the substrate was smoothed to prevent the formation of pinholes in the alloy film, and the alloy film had an appropriate content ratio to alloy Au with Ta, so even in an aqueous sulfuric acid solution. In the immersion, the adhesion to the metal substrate is not impaired, and the alloy film is not aggregated, and the alloy film is excellent in corrosion resistance, so that good results can be obtained -37-200843180 <Example 3 9 &gt; Metal of the present invention The separators were incorporated in a fuel cell to perform a power generation test. The metal separators were fabricated in the following order. First, as shown in Fig. 2(A), a gas flow having a groove width of 0.6 mm and a groove depth of 0.5 mm is machined at the central portion of the surface of the metal substrate 2 composed of a titanium plate (95·2 χ 95·2 χ 19 mm). Road 21. The gas flow path 21 has gas inlet ports 22 for introducing hydrogen gas or air at both ends thereof. When the alloy film is formed into a film, an Au-Ta alloy target is produced and used to form a film. The powder of Au and Ta was mixed so that the Au composition was 60 atom%, and the molding was carried out in the order of mold filling, mold degassing, HIP, demolding, forging, calendering, and machining, and the outer diameter was 152.4 mm (6 inches).吋), a 5 mm thick disc-shaped sputter target. Then, on the surface of the metal substrate 2 on which the gas flow path 21 is formed, the An-Ta sputtering target is used, and the film formation conditions are the same as those in the first embodiment, and Au and Ta are formed so as to have a film thickness of 20 mm. The alloy film formed. Further, when the film formation on the pure titanium substrate was carried out under the conditions of the sputtering target, the Au composition in the alloy film was measured by ICP emission spectrometry, and it was confirmed that the composition was about the same as the target composition of 61 atomic %. Then, the metal substrate 2 on which the alloy film composed of Au and Ta was formed was heat-treated at 500 ° C for 5 minutes in a vacuum atmosphere of 0.00665 Pa to produce a metal separator. Then, as shown in Fig. 3, the metal separators 3 1 and 3 1 were placed in a single-cell battery 10 of a commercially available fuel cell (EFC-05-01SP) -38 - 200843180 20 manufactured by Electrochem. In the fuel cell shown in Fig. 3, a 32-series solid polymer membrane and a 33-series carbon cloth were used. Then, 99.999% of hydrogen gas was used as the anode side fuel gas, and air was used as the cathode side gas to carry out a power generation test. At this time, the fuel cell was heated to 80 ° C in total, and hydrogen gas and air were introduced into the heated water to adjust the dew point temperature to 80 ° C, and introduced into the fuel cell at a pressure of 2026 hPa (2 atmospheres). Next, using a battery performance measuring system (890CL manufactured by Scribner Co., Ltd.), a current flowing into the separator was used as a power of 300 mA/cm2 for 100 hours to measure changes in voltage and output. As a result, the voltage at the initial stage of power generation of the separator of the titanium substrate and the voltage after power generation for 100 hours were both 0.61 V, and no change in voltage was observed. In addition, a fuel cell was fabricated by using a graphite separator (FC05-MP, manufactured by Electrochem Co., Ltd.), which was used in the past, in place of the separator of the titanium substrate, and the power generation test was carried out under the same conditions as described above. As a result, the voltage at the initial stage of power generation and the voltage after 100 hours of power generation were both 0.61 V, which was the same result as the separator of the titanium substrate. From the above results, it is understood that the separator produced by the method for producing a fuel cell separator of the present invention exhibits performance equivalent to that of the graphite separator even in the case of a metal separator. The present invention will be described in detail with reference to the particular embodiments of the invention. In addition, this application is based on the Japan-licensed application filed on December 21, 2006 (Japanese Patent Application No. 2006-344895) and the Japanese Patent Application filed on September 21, 2007 (Special Wish 2007) -2459 1 7 ), all of which are cited by reference. All of the reference frames cited herein are also taken in. Industrial Applicability According to the present invention, it is possible to provide a metal of a fuel cell which is excellent in corrosion resistance and low in contact resistance, and can maintain its low contact resistance even in a corrosive environment for a long period of time. An alloy film for a separator, a method for producing the same, a target material for sputtering, a metal separator, and a fuel cell. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the steps of a method for producing a metal separator for a fuel cell of the present invention. Fig. 2 (A) is a plan view of a metal separator for a fuel cell of the present invention. (B) is a partially enlarged cross-sectional view of a metal separator for a fuel cell. Fig. 3 is an exploded cross-sectional view showing the configuration of a fuel cell using the metal separator for a fuel cell of the present invention. Fig. 4 is a view for explaining a method of measuring contact resistance. [Main component symbol description] S 1 : formation step 52: setting step 53: film formation step -40 - 200843180 Reference: heat treatment step 3 1 : metal separator metal substrate alloy film: single cell: fuel cell: gas flow path: Gas introduction port: solid polymer film: carbon cloth: test plate: carbon cloth: copper electrode: DC current power supply: voltmeter-41

Claims (1)

200843180 十、申請專利範圍 1 · 一種燃料電池之金屬隔板用合金被膜’ 於：含有選自All及pt之至少一種貴金屬元素、 Ti、Zr、Nb、Hf及Ta所構成之群中的至少一種 屬元素，前述貴金屬元素/非貴金屬元素之含有 子比爲35/65〜95/5，膜厚爲2 nm以上。 2·燃料電池之金屬隔板用合金被膜之製造 特徵在於含有： 設置步驟，其係於實施濺鍍法之裝置的腔室 屬基板； 成膜步驟，其係於在前述設置步驟中所設置 屬基板表面的至少一部份藉濺鍍法而形成合金被 金被膜係使選自Au及Pt之至少一種貴金屬元素 由Ti、Zr、Nb、Hf及Ta所構成之群中的至少一 金屬元素，以貴金屬元素/非貴金屬元素之含有 子比爲3 5/65〜9 5/5之比率含有，且膜厚爲2nm以 3 ·如申請專利範圍第2項之燃料電池之金 合金被膜之製造方法，其中前述成膜步驟後，進 使形成前述合金被膜之金屬基板進行熱處理之熱 〇 4 ·如申請專利範圍第3項之燃料電池之金 合金被膜之製造方法，其中在前述熱處理步驟中 的溫度爲150〜800°C。 5 .如申請專利範圍第4項之燃料電池之金 其特徵在 與選自由 之非貴金 比率就原 方法，其 內設置金 之前述金 膜，該合 、與選自 種之非貴 比率就原 上。 屬隔板用 一步含有 處理步驟 屬隔板用 之熱處理 屬隔板用 -42 - 200843180 合金被膜之製造方法，其中使前述熱處理在具有 104Pa以下之氧分壓的環境下實施。 6·如申請專利範圍第2項之燃料電池之金屬隔 合金被膜之製造方法，其中前述成膜步驟係使前述金 板加熱至150〜800°C而進行。 7· —種燃料電池之金屬隔板用合金被膜，其特 於：以如申請專利範圍第2〜6項中任一項之製造方法 〇 8· —種燃料電池用金屬隔板，其特徵在於：於 基板之表面形成如申請專利範圍第1〜7項中任一項之 隔板用合金被膜而得到。 9·如申請專利範圍第8項之燃料電池用金屬隔 前述金屬基板形成凹部，該凹部係於其表面之至少一 形成流通氣體之氣體流路。 1 〇 ·如申請專利範圍第8或9項之燃料電池用金 板，其中前述金屬基板爲由選自鈦、鈦基合金、、 合金及不鏽鋼所構成之群中的至少一種的金屬所構成 11. 一種燃料電池用金屬隔板之製造方法，其特 於含有： 設置步驟，其係於實施濺鍍法之裝置的腔室Θ設 屬基板； 成膜步驟，其係於在前述設置步驟中所設置之_ 屬基板表面藉濺鍍法形成合金被膜，該合金被膜係、t 自Au及Pt之至少一種貴金屬元素、與選自由Ti、 2.1 X 板用 屬基 徵在 製造 金屬 金屬 板， 部份 屬隔 鋁基 〇 徵在 置金 述金 -i=r 々BB Zr、 -43- 200843180 Nb、Hf及Ta所構成之群中的至少一種之非貴金屬元素， 前述貴金屬元素/非貴金屬元素之含有比率就原子比爲 35/65〜95/5’膜厚爲2nm以上。 1 2·如申請專利範圍第1 1項之燃料電池用金屬隔板 之製造方法，其中前述設置步驟之前，含有形成步驟，前 述形成步驟係前述金屬基板之表面的至少一部份形成用以 形成流通氣體之氣體流路之凹部。 1 3 ·如申請專利範圍第丨1或丨2項之燃料電池用金屬 隔板之製造方法，其中前述成膜步驟後，進一步含有使形 成前述合金被膜之金屬基板進行熱處理之熱處理步驟。 1 4 .如申請專利範圍第1 3項之燃料電池用金屬隔板 之製造方法，其中前述熱處理的溫度爲150〜800°C。 1 5 .如申請專利範圍第1 4項之燃料電池用金屬隔板 之製造方法，其中使前述熱處理在具有2.1xl04Pa以下之 氧分壓的環境下實施。 1 6 ·如申請專利範圍第1 1項之燃料電池用金屬隔板 之製造方法，其中前述成膜步驟係使前述金屬基板加熱至 150〜800°C而進行。 1 7 · —種燃料電池，其特徵在於：具備以如申請專利 範圍第8〜1 0項中任一項之燃料電池用金屬隔板。 1 8 . —種濺鍍用標靶材料，係使用於燃料電池之金屬 隔板用合金被膜之製造，其特徵在於：由選自Au及Pt之 至少一種貴金屬元素、與選自由Ti、Zr、Nb、Hf及Ta所 構成之群中的至少一種之非貴金屬元素所成，兩者之原子 -44- 200843180 95/5。 比（貴金屬元素/非貴金屬元素）爲35/65200843180 X. Patent Application No. 1 - An alloy film for a metal separator for a fuel cell": at least one selected from the group consisting of at least one noble metal element selected from All and pt, Ti, Zr, Nb, Hf, and Ta The genus element has a content ratio of the noble metal element/non-precious metal element of 35/65 to 95/5 and a film thickness of 2 nm or more. 2. The alloy film for a metal separator for a fuel cell is characterized by comprising: a setting step of a chamber substrate to which a sputtering method is applied; and a film forming step of the genus set in the aforementioned setting step At least a portion of the surface of the substrate is formed by a sputtering method to form at least one metal element selected from the group consisting of Ti, Zr, Nb, Hf, and Ta by at least one noble metal element selected from the group consisting of Au and Pt. A method for producing a gold alloy film of a fuel cell according to the second aspect of the invention, wherein the ratio of the content of the noble metal element to the non-precious metal element is 3 5/65 to 9 5/5, and the film thickness is 2 nm to 3 After the film forming step, the heat treatment of the metal substrate forming the alloy film is performed. The method of manufacturing the gold alloy film of the fuel cell according to claim 3, wherein the temperature in the heat treatment step is It is 150~800 °C. 5. The gold of the fuel cell according to item 4 of the patent application is characterized in that it is based on the non-precious gold ratio selected from the original method, and the gold film is provided in the gold film, and the non-expensive ratio of the combination and the selected species is Originally. It is a step of containing a separator. The heat treatment for the separator is a separator. The method for producing an alloy coating is carried out in an environment having an oxygen partial pressure of 104 Pa or less. 6. The method of producing a metal barrier alloy film for a fuel cell according to the second aspect of the invention, wherein the film forming step is performed by heating the gold plate to 150 to 800 °C. An alloy film for a metal separator for a fuel cell, which is characterized by the method of manufacturing a fuel cell according to any one of claims 2 to 6, wherein the metal separator for a fuel cell is characterized in that An alloy film for a separator according to any one of the first to seventh aspects of the invention is obtained on the surface of the substrate. 9. The fuel cell metal separator according to the eighth aspect of the invention, wherein the metal substrate forms a concave portion, and the concave portion is formed on at least one of the surfaces thereof to form a gas flow path for flowing gas. The gold plate for a fuel cell according to claim 8 or 9, wherein the metal substrate is made of a metal selected from the group consisting of titanium, a titanium-based alloy, an alloy, and a stainless steel. A method for producing a metal separator for a fuel cell, comprising: a setting step of: a chamber for a device for performing a sputtering method; and a film forming step of the step of forming The surface of the substrate is formed by sputtering to form an alloy film, the alloy film, at least one precious metal element from Au and Pt, and a metal metal plate selected from the group consisting of Ti and 2.1 X plates. a non-precious metal element of at least one of the group consisting of a gold-based ruthenium in the group of gold, i=r=々 BB Zr, -43- 200843180 Nb, Hf and Ta, the content of the aforementioned precious metal element/non-precious metal element The ratio is an atomic ratio of 35/65 to 95/5' and the film thickness is 2 nm or more. The method for manufacturing a metal separator for a fuel cell according to the first aspect of the invention, wherein the step of forming includes a forming step of forming at least a portion of a surface of the metal substrate to form a recess of the gas flow path through which the gas flows. The method for producing a metal separator for a fuel cell according to the first or second aspect of the invention, wherein the film forming step further comprises a heat treatment step of heat-treating the metal substrate forming the alloy film. The method for producing a metal separator for a fuel cell according to the first aspect of the invention, wherein the temperature of the heat treatment is 150 to 800 °C. The method of producing a metal separator for a fuel cell according to claim 14 wherein the heat treatment is carried out in an environment having an oxygen partial pressure of 2.1 x 10 Pa or less. The method of producing a metal separator for a fuel cell according to the first aspect of the invention, wherein the film forming step is performed by heating the metal substrate to 150 to 800 °C. A fuel cell for a fuel cell according to any one of claims 8 to 10 of the patent application. The invention relates to a target material for sputtering, which is produced by using an alloy film for a metal separator for a fuel cell, characterized by comprising at least one noble metal element selected from the group consisting of Au and Pt, and selected from the group consisting of Ti and Zr. A non-noble metal element of at least one of the group consisting of Nb, Hf, and Ta, the atom of which is -44-200843180 95/5. Ratio (precious metal element / non-precious metal element) is 35/65 •45-•45-
TW096149425A 2006-12-21 2007-12-21 Alloy coating film for metal separator of fuel cell, method for producing the same, sputtering target material, metal separator and fuel cell TW200843180A (en)

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JP2007245917A JP4134257B2 (en) 2006-12-21 2007-09-21 Alloy film for metal separator of fuel cell, production method thereof, sputtering target material, metal separator and fuel cell

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