JP2001006713A - Low contact-resistance stainless steel, titanium, and carbon material, for proton-exchange membrane fuel cell member - Google Patents
Low contact-resistance stainless steel, titanium, and carbon material, for proton-exchange membrane fuel cell memberInfo
- Publication number
- JP2001006713A JP2001006713A JP11170142A JP17014299A JP2001006713A JP 2001006713 A JP2001006713 A JP 2001006713A JP 11170142 A JP11170142 A JP 11170142A JP 17014299 A JP17014299 A JP 17014299A JP 2001006713 A JP2001006713 A JP 2001006713A
- Authority
- JP
- Japan
- Prior art keywords
- contact resistance
- noble metal
- fuel cell
- stainless steel
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電力を直接的駆動
源とする自動車、小規模の発電システムなどに用いられ
る固体高分子型燃料電池部材用材料に関する。さらに詳
しくは、その接触抵抗を低くするために、表面に処理を
施した固体高分子型燃料電池部材用低接触抵抗材料に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for a polymer electrolyte fuel cell member used for automobiles and small-scale power generation systems that use electric power as a direct drive source. More specifically, the present invention relates to a low contact resistance material for a polymer electrolyte fuel cell member whose surface has been treated to reduce its contact resistance.
【０００２】[0002]
【従来の技術】近年電気自動車用燃料電池の開発が、固
体高分子材料の開発成功を契機に急速に進展し始めてい
る。固体高分子型燃料電池とは、従来のアルカリ型燃料
電池、燐酸型燃料電池、溶融炭酸塩型燃料電池、固体電
解質型燃料電池などとは異なり、水素イオン選択透過型
の有機物膜を電解質として用いることを特徴とする燃料
電池である。2. Description of the Related Art In recent years, the development of fuel cells for electric vehicles has begun to progress rapidly with the successful development of solid polymer materials. Unlike polymer electrolyte fuel cells, which are different from conventional alkaline fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, solid electrolyte fuel cells, etc., they use a hydrogen ion selective permeation type organic material membrane as the electrolyte. It is a fuel cell characterized by the above.
【０００３】固体高分子型燃料電池の燃料には、純水素
のほかアルコール類の改質によって得た水素ガスなどを
用い、空気中の酸素との反応を電気化学的に制御するこ
とによって、電力を取り出すシステムである。固体高分
子膜は薄くても十分に機能し、電解質が膜中に固定され
ていることから、電池内の露点を制御すれば電解質とし
て機能するために、水溶液系電解質や溶融塩系電解質な
ど流動性のある媒体を使う必要がなく、電池自体をコン
パクトに単純化して設計できることも特徴である。As a fuel for a polymer electrolyte fuel cell, pure hydrogen and hydrogen gas obtained by reforming alcohols and the like are used, and the reaction with oxygen in the air is electrochemically controlled to produce electric power. It is a system to take out. Solid polymer membranes function well even if they are thin, and since the electrolyte is fixed in the membrane, they can function as electrolytes if the dew point in the battery is controlled, so fluids such as aqueous electrolytes and molten salt electrolytes can be used. There is no need to use versatile media, and the battery itself can be designed to be compact and simple.
【０００４】従来、燃料電池用ステンレス鋼としては、
特開平４−２４７８５２号公報で開示された溶融炭酸塩
型燃料電池用耐食ステンレス鋼、特開平４−３５８０４
４号公報で開示された溶融炭酸塩型燃料電池セパレータ
用高耐食鋼板、特開平７−１８８８７０号公報で開示さ
れた溶融塩に対する耐食性に優れたステンレス鋼および
その製造方法、特開平８−１６５５４６号公報で開示さ
れた耐溶融炭酸塩性に優れたステンレス鋼、特開平８−
２２５８９２号公報で開示された耐溶融炭酸塩腐食性に
優れたステンレス鋼、及び特開平８−３１１４６２０号
公報で開示された熱間加工性及び耐溶融塩腐食性に優れ
たステンレス鋼などが公知である。Conventionally, as stainless steel for fuel cells,
Japanese Patent Laid-Open No. 4-247852 discloses a corrosion-resistant stainless steel for molten carbonate fuel cells.
No. 4 discloses a high corrosion-resistant steel plate for a molten carbonate fuel cell separator, a stainless steel disclosed in JP-A-7-188870 having excellent corrosion resistance to molten salts and a method for producing the same, and JP-A-8-165546. Japanese Patent Laid-Open Publication No. Hei 8-
Known are stainless steel excellent in molten carbonate corrosion resistance disclosed in JP-A-225892 and stainless steel excellent in hot workability and molten salt corrosion resistance disclosed in JP-A-8-3114620. is there.
【０００５】また、高い耐食性が要求される溶融炭酸塩
環境で稼動する燃料電池用ステンレス鋼として、特開平
６−２６４１９３号公報および特開平６−２９３９４１
号公報で開示された固体電解質型燃料電池用金属材料、
特開平９−６７６７２号公報で開示されたフェライト系
ステンレス鋼など、数百度の高温で稼動する固体電解質
型燃料電池材料の発明がなされている。Further, as a stainless steel for a fuel cell which operates in a molten carbonate environment where high corrosion resistance is required, JP-A-6-264193 and JP-A-6-293941.
Metal material for a solid oxide fuel cell disclosed in
A solid electrolyte fuel cell material which operates at a high temperature of several hundred degrees, such as a ferritic stainless steel disclosed in Japanese Patent Application Laid-Open No. 9-67672, has been invented.
【０００６】これに対して、１００℃以下の領域で稼動
する固体高分子型燃料電池の構成材料としては、温度が
さほど高くないこと、およびその環境下で耐食性・耐久
性を十分発揮させることが可能であることなどの理由
で、炭素系の材料が使用されてきており、このタイプの
燃料電池へのステンレス鋼やチタンなど金属系の材料の
適用は検討されていなかった。On the other hand, as a constituent material of a polymer electrolyte fuel cell which operates at a temperature of 100 ° C. or lower, it is required that the temperature is not so high and that the corrosion resistance and durability under the environment are sufficiently exhibited. Carbon-based materials have been used for reasons such as being possible, and application of metal-based materials such as stainless steel and titanium to this type of fuel cell has not been considered.
【０００７】[0007]
【発明が解決しようとする課題】固体高分子型燃料電池
は、電解質となる固体高分子膜の両面に炭素微粒子と貴
金属超微粒子からなる触媒電極部、そこで発生する電力
を電流として取り出すと同時に触媒電極部へ反応ガスを
供給する機能を持った、フェルト状炭素繊維集合体（通
称カーボンペーパー）からなるカレントコレクター、そ
こからの電流を受けると共に酸素主体および水素主体の
２種の反応ガスや冷却媒体を分離するセパレーターなど
が積層されることにより構成される。The polymer electrolyte fuel cell has a catalyst electrode portion composed of carbon fine particles and noble metal ultrafine particles on both surfaces of a solid polymer membrane serving as an electrolyte. A current collector consisting of a felt-like carbon fiber aggregate (commonly known as carbon paper) having a function of supplying a reaction gas to the electrode section. It receives current from it and has two types of reaction gas and cooling medium mainly composed of oxygen and hydrogen. Is formed by stacking a separator or the like that separates the components.
【０００８】従来、このセパレーターにも炭素材料が使
用されていたが、自動車への搭載を考慮した場合、コス
トが高い、電池の大きさが大きいといった問題点があ
り、セパレーターなどの部材へのステンレス鋼の適用が
検討され始めている。Conventionally, carbon materials have also been used for this separator. However, considering the mounting on automobiles, there are problems such as high cost and large size of the battery. The application of steel is beginning to be considered.
【０００９】本発明者らは、既に特願平１１−６１１４
６号や特願平１１−６２８１３号により、ステンレス鋼
をセパレータなどの固体高分子型燃料電池用部材として
使用するための具体的形状や成分などを開示している
が、ステンレス鋼製またはチタン製セパレータにおいて
は、カレントコレクターとなるカーボンペーパーとの接
触抵抗が大きいため、燃料電池としてのエネルギー効率
を大幅に低下させることが問題として指摘され始めてい
る。The present inventors have already filed Japanese Patent Application No. 11-6114.
No. 6 and Japanese Patent Application No. 11-62813 disclose specific shapes and components for using stainless steel as a member for a polymer electrolyte fuel cell such as a separator. Since the separator has a large contact resistance with the carbon paper serving as a current collector, it has begun to be pointed out as a problem that the energy efficiency of the fuel cell is greatly reduced.
【００１０】本発明は、かかる状況に鑑み、使用される
素材間の接触抵抗を検討し、固体高分子型燃料電池のエ
ネルギー変換効率を最大限に発揮させるための固体高分
子型燃料電池部材用の低接触抵抗材料を提供することを
目的とする。In view of such circumstances, the present invention considers the contact resistance between materials to be used, and provides a polymer electrolyte fuel cell member for maximizing the energy conversion efficiency of the polymer electrolyte fuel cell. An object of the present invention is to provide a low contact resistance material.
【００１１】[0011]
【課題を解決するための手段】本発明は、上記課題を解
決するためになされたもので、その要旨とするところは
次の通りである。 （１）他の部材と接触し接触抵抗を生ずる部分に、貴金
属または貴金属の合金が付着されていることを特徴とす
る固体高分子型燃料電池部材用低接触抵抗ステンレス
鋼。 （２）表面の酸化皮膜を除去した後に、貴金属または貴
金属の合金が付着されていることを特徴とする前記
（１）に記載の固体高分子型燃料電池部材用低接触抵抗
ステンレス鋼。 （３）貴金属または貴金属の合金の平均厚さが、５ｎｍ
以上であることを特徴とする前記（１）または（２）に
記載の固体高分子型燃料電池部材用低接触抵抗ステンレ
ス鋼。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and the gist thereof is as follows. (1) A low contact resistance stainless steel for a polymer electrolyte fuel cell member, wherein a noble metal or an alloy of a noble metal is adhered to a portion which comes into contact with another member and generates contact resistance. (2) The low contact resistance stainless steel for a polymer electrolyte fuel cell member according to (1), wherein a noble metal or a noble metal alloy is adhered after removing the oxide film on the surface. (3) The average thickness of the noble metal or alloy of the noble metal is 5 nm
The low contact resistance stainless steel for a polymer electrolyte fuel cell member according to the above (1) or (2), characterized by the above.
【００１２】（４）他の部材と接触し接触抵抗を生ずる
部分に、貴金属または貴金属の合金が付着されているこ
とを特徴とする固体高分子型燃料電池部材用低接触抵抗
チタン。 （５）表面の酸化皮膜を除去した後に、貴金属または貴
金属の合金が付着されていることを特徴とする前記
（４）に記載の固体高分子型燃料電池部材用低接触抵抗
チタン。 （６）貴金属または貴金属の合金の平均厚さが、５ｎｍ
以上であることを特徴とする前記（４）または（５）に
記載の固体高分子型燃料電池部材用低接触抵抗チタン。(4) A low contact resistance titanium for a polymer electrolyte fuel cell member, wherein a noble metal or an alloy of a noble metal is adhered to a portion which comes into contact with another member and generates contact resistance. (5) The low contact resistance titanium for a polymer electrolyte fuel cell member according to (4), wherein a noble metal or an alloy of a noble metal is adhered after removing an oxide film on the surface. (6) The average thickness of the noble metal or alloy of the noble metal is 5 nm
The low contact resistance titanium for a polymer electrolyte fuel cell member according to the above (4) or (5), which is characterized by the above.
【００１３】（７）他の部材と接触し接触抵抗を生ずる
部分に、貴金属または貴金属の合金が付着されているこ
とを特徴とする固体高分子型燃料電池部材用低接触抵抗
炭素材料。 （８）表面の酸化皮膜を除去した後に、貴金属または貴
金属の合金が付着されていることを特徴とする前記
（７）に記載の固体高分子型燃料電池部材用低接触抵抗
炭素材料。 （９）貴金属または貴金属の合金の平均厚さが、５ｎｍ
以上であることを特徴とする前記（７）または（８）に
記載の固体高分子型燃料電池部材用低接触抵抗炭素材
料。(7) A low contact resistance carbon material for a polymer electrolyte fuel cell member, wherein a noble metal or an alloy of a noble metal is adhered to a portion which comes into contact with another member and generates contact resistance. (8) The low contact resistance carbon material for a polymer electrolyte fuel cell member according to (7), wherein a noble metal or a noble metal alloy is adhered after removing the oxide film on the surface. (9) The average thickness of the noble metal or alloy of the noble metal is 5 nm
The low contact resistance carbon material for a polymer electrolyte fuel cell member according to the above (7) or (8), which is characterized by the above.
【００１４】[0014]
【発明の実施の形態】接触抵抗の測定法として、直径３
０mmの円盤状の電流供給面をもつ治具を上下に配し、そ
の間に２個の直径３０mm、厚さ４mmの円盤状金属試験片
やカーボンペーパーを挟み込み、接触面の面圧が２．７
９kg／cm2 となるよう上部に錘を乗せ、電流密度１．１
３Ａ／cm2 の定電流を供給して、２個の円盤状金属試験
片間の電位差を測定することにより、接触抵抗を求め
た。BEST MODE FOR CARRYING OUT THE INVENTION As a method of measuring a contact resistance, a diameter 3
A jig having a disk-shaped current supply surface of 0 mm is arranged vertically, and two disk-shaped metal test pieces of 30 mm in diameter and 4 mm in thickness and carbon paper are sandwiched between the jigs, and the surface pressure of the contact surface is 2.7.
A weight is placed on the upper part so as to be 9 kg / cm 2, and the current density is 1.1
The contact resistance was determined by supplying a constant current of 3 A / cm 2 and measuring the potential difference between the two disc-shaped metal test pieces.
【００１５】円盤状金属試験片の材質として、３０μｍ
金めっきをした銅、市販のステンレス鋼であるＳＵＳ３
１６Ｌ、ＹＵＳ２７０、ＹＵＳ２６０、ＹＵＳ１９０
Ｌ、および工業用第１種純チタンを選定した（ＹＵＳは
新日本製鐵株式会社規格）。また、カーボンペーパーに
は、燃料電池用にガス透過性と電気伝導性の観点から最
適とされた厚さ０．６mmの試作品を１種類選定し、一片
３０mmの正方形に切り出し試験に供した。まず標準値を
得るために、ステンレス鋼およびチタン製試験片は接触
面を鏡面研磨仕上げしたものを用い、接触抵抗測定を行
った。The material of the disc-shaped metal test piece is 30 μm
Gold plated copper, SUS3, a commercially available stainless steel
16L, YUS270, YUS260, YUS190
L and industrial grade 1 pure titanium were selected (YUS is Nippon Steel Corporation standard). As the carbon paper, one prototype having a thickness of 0.6 mm, which was optimized from the viewpoint of gas permeability and electric conductivity for a fuel cell, was selected and cut into a 30 mm square piece for the test. First, in order to obtain a standard value, the contact resistance was measured using a stainless steel and titanium test piece having a mirror-polished contact surface.
【００１６】その結果、接触抵抗の値はｍΩ・cm2 で、
金／金：０．０２、 金／カーボンペーパー：５．３
０、 金／ＳＵＳ３１６Ｌ：２２．４３、 ＳＵＳ３１
６Ｌ／ＳＵＳ３１６Ｌ：５４．９０、チタン／カーボン
ペーパー：５６６．８３、 ＹＵＳ２７０／カーボンペ
ーパー：６９６．５０、 ＹＵＳ２６０／カーボンペー
パー：６７９．８７、ＹＵＳ１９０Ｌ／カーボンペーパ
ー：８１９．４０、 ＳＵＳ３１６Ｌ／カーボンペーパ
ー：６１４．５２という値を得た。As a result, the value of the contact resistance is mΩ · cm 2 ,
Gold / gold: 0.02, gold / carbon paper: 5.3
0, Fri / SUS316L: 22.43, SUS31
6L / SUS316L: 54.90, titanium / carbon paper: 566.83, YUS270 / carbon paper: 696.50, YUS260 / carbon paper: 679.87, YUS190L / carbon paper: 819.40, SUS316L / carbon paper: 614 .52 was obtained.
【００１７】なお、金／カーボンペーパーの接触抵抗は
カーボンペーパーを２枚の金めっき銅円盤状試験片で挟
み、金めっき銅円盤状試験片間の電位差を電流密度で除
算した後、２で割って値を得たため、カーボンペーパー
の厚み半分の抵抗値も含まれる。また、ステンレス鋼や
チタンとカーボンペーパーとの接触抵抗値は、ステンレ
ス鋼またはチタン／カーボンペーパー／金めっき銅の組
合せの両端で電位差を測定して、電流密度で除算して得
た全抵抗値から金／カーボンペーパーの接触抵抗値を差
し引くことによって求めた。The contact resistance of the gold / carbon paper is obtained by sandwiching the carbon paper between two gold-plated copper disc-shaped test pieces, dividing the potential difference between the gold-plated copper disc-shaped test pieces by the current density, and dividing by two. Therefore, the resistance value of half the thickness of the carbon paper is also included. The contact resistance between stainless steel or titanium and carbon paper is calculated from the total resistance obtained by measuring the potential difference at both ends of the stainless steel or titanium / carbon paper / gold plated copper combination and dividing by the current density. It was determined by subtracting the contact resistance value of the gold / carbon paper.
【００１８】これらの結果を整理すると、 金／金および金／カーボンペーパーの接触面では殆
ど抵抗は生じない。 ステンレス鋼やチタンには酸化皮膜が存在するため
に、数十ｍΩ・cm2 程度の接触抵抗が生じる。 ステンレス鋼またはチタンとカーボンペーパーとの
接触面には、オームの法則では予想できないほど大きな
接触抵抗が生ずる。 という３点が判明した。Summarizing these results, almost no resistance occurs at the gold / gold and gold / carbon paper contact surfaces. Due to the presence of an oxide film on stainless steel and titanium, a contact resistance of about several tens mΩ · cm 2 is generated. The contact surface between the stainless steel or titanium and the carbon paper has a contact resistance that is unexpectedly large according to Ohm's law. Three points were found.
【００１９】この現象は、カーボンペーパーを構成する
黒鉛の電気伝導が共役二重結合を行っているπ電子によ
り行われていることと深く関係し、黒鉛より大幅に差異
のある仕事関数値をもつステンレス鋼やチタンとの接触
界面には、いわゆるショットキー障壁が形成されたた
め、大きな接触抵抗を生じたものと考えられる。This phenomenon is closely related to the fact that the electrical conductivity of graphite constituting carbon paper is performed by π electrons having a conjugated double bond, and has a work function value that is significantly different from that of graphite. It is considered that a so-called Schottky barrier was formed at the contact interface with stainless steel or titanium, which caused a large contact resistance.
【００２０】このように半導体物理学的に接触抵抗問題
を考察すると、今回観測されたデータが矛盾なく説明で
きることから、黒鉛と同等の仕事関数値を有する貴金属
（ここでは、金，白金，パラジウム，銀，銅，錫，鉛な
どを指すものとする）、またはこれらの金属の合金をス
テンレス鋼またはチタンとカーボンペーパー接触面の間
に挟みこむことで、接触抵抗を低減できるという指針が
得られた。Considering the contact resistance problem in terms of semiconductor physics as described above, the data observed this time can be explained without contradiction. Therefore, noble metals (here, gold, platinum, palladium, The guideline was obtained that the contact resistance could be reduced by inserting silver, copper, tin, lead, etc.) or an alloy of these metals between stainless steel or titanium and the carbon paper contact surface. .
【００２１】一方、ステンレス鋼やチタンには酸化皮膜
がごく薄く存在することが知られているが、この皮膜も
接触抵抗を上昇させる原因となることが実験により判明
した。これについては、皮膜を除去しながら貴金属を付
着させることでカーボンペーパーとの接触抵抗を低減す
ることが指針となる。On the other hand, it is known that stainless steel and titanium have an extremely thin oxide film, but it has been found through experiments that this film also causes an increase in contact resistance. The guideline for this is to reduce the contact resistance with carbon paper by attaching a noble metal while removing the film.
【００２２】そこで、カーボンペーパーの接触面側にイ
オンプレーティング法により金をコーティングして鏡面
研摩したステンレス鋼との接触抵抗低減効果を測定した
ところ、蒸着速度と蒸着時間から換算した平均厚さで５
ｎｍ以上の金が付着すると接触抵抗が低減し始めること
がわかった。Then, when the contact surface side of the carbon paper was coated with gold by an ion plating method and the effect of reducing the contact resistance with the stainless steel polished to a mirror surface was measured, the average thickness converted from the deposition rate and the deposition time was measured. 5
It has been found that when gold of nm or more adheres, the contact resistance starts to decrease.
【００２３】また、ステンレス鋼を、０．５％塩化白金
酸を含む１Ｎ塩酸水溶液中で耐水型のシリコンカーバイ
ド紙により軽く研摩して、不働態皮膜を機械的に除去し
ながらメタル表面に白金を腐食反応により微量析出させ
る処理を行い、無処理のカーボンペーパーとの接触抵抗
を測定したところ、やはり平均厚さで５ｎｍ以上の白金
が付着していると接触抵抗が低減し始める効果が認めら
れた。Also, stainless steel is lightly polished with a water-resistant silicon carbide paper in a 1N hydrochloric acid aqueous solution containing 0.5% chloroplatinic acid to remove platinum on the metal surface while mechanically removing the passive film. When a treatment for precipitating a small amount by the corrosion reaction was performed and the contact resistance with the untreated carbon paper was measured, it was confirmed that the contact resistance began to decrease when platinum having an average thickness of 5 nm or more was adhered. .
【００２４】さらに本発明の効果を確認するために、ス
テンレス鋼，チタン，カーボンペーパーに種々の表面処
理を施して、それらの組合わせ接触面における接触抵抗
を測定した結果を表１（表１−１〜表１−４）に示す。Further, in order to confirm the effect of the present invention, various surface treatments were applied to stainless steel, titanium, and carbon paper, and the results of measuring the contact resistance at the combined contact surfaces were shown in Table 1 (Table 1). 1 to Table 1-4).
【００２５】組合せ番号１〜２９までは、ステンレス鋼
には表面処理をせず、カーボンペーパーに金，白金，パ
ラジウム，鉛，錫，銅，ニッケルをイオン蒸着法または
電解メッキ法により付与したものである。これらの結果
から、いずれも５ｎｍ以上の平均厚さを確保すれば接触
抵抗が低減すること、表面処理平均厚さを厚くするほど
接触抵抗が低減すること、などが無処理材（組合せ番号
１＝基準１）と比較することによりわかる。Combination Nos. 1 to 29 are those in which no surface treatment is applied to stainless steel and carbon, gold, platinum, palladium, lead, tin, copper and nickel are applied by ion vapor deposition or electrolytic plating. is there. From these results, it can be seen that the contact resistance is reduced if the average thickness of 5 nm or more is secured, and that the contact resistance is reduced as the average thickness of the surface treatment is increased. It can be seen by comparing with criterion 1).
【００２６】組合せ番号３０〜５６までは、カーボンペ
ーパーにイオン蒸着により１０００ｎｍの金を付着した
表面に、各種ステンレス鋼およびチタンの酸化皮膜を機
械的に除去しながら貴金属を析出または付着させた面を
接触させて、接触抵抗を測定した結果である。これらの
結果から、いずれのステンレス鋼およびチタンにおいて
も、これらの処理を施すことによって接触抵抗が低減す
ることがわかる。For combinations Nos. 30 to 56, the surface on which noble metal was deposited or adhered while mechanically removing oxide films of various stainless steels and titanium on the surface of carbon paper to which gold of 1000 nm was adhered by ion vapor deposition. It is the result of having measured contact resistance after making contact. From these results, it is understood that the contact resistance is reduced by performing these treatments on any of stainless steel and titanium.
【００２７】皮膜除去しながら貴金属を析出または付着
させる方法として、ここでは０．５％塩化白金酸を含む
１Ｎ塩酸水溶液中で耐水型のシリコンカーバイド紙によ
り軽く研摩し、腐食反応により白金などを微量析出させ
る方法、同様な研摩後カソード電解によってより多くの
白金の析出を促す方法、あるいは金，銀などを無電解メ
ッキしたガラスビーズでブラスト処理する方法などを試
みたが、いずれも接触抵抗を低減する効果が観測され
た。As a method of precipitating or adhering a noble metal while removing the film, here, lightly polished with a water-resistant silicon carbide paper in a 1N hydrochloric acid aqueous solution containing 0.5% chloroplatinic acid, and a trace amount of platinum or the like is removed by a corrosion reaction. We tried a method of depositing, a method of promoting more platinum deposition by cathodic electrolysis after polishing, or a method of blasting with gold or silver electroless plated glass beads, all of which reduced contact resistance Effect was observed.
【００２８】組合せ番号５７〜７３は、ステンレス鋼同
士、またはチタン同士、またはステンレス鋼とチタンの
接触面における接触抵抗を調べた結果である。これらの
接触抵抗低減率は、組合せ番号５７の無処理表面同士の
接触抵抗を基準（基準２）として算出した。いずれも接
触抵抗低減効果があることが実証できた。Combination numbers 57 to 73 are the results of examining the contact resistance at the contact surface between stainless steel, between titanium, or between stainless steel and titanium. These contact resistance reduction rates were calculated using the contact resistance between the untreated surfaces of combination number 57 as a reference (reference 2). It was proved that each of them had a contact resistance reduction effect.
【００２９】なお、本発明の貴金属もしくは貴金属の合
金の付着は、相接触する両面においてされていることが
望ましい。また、貴金属もしくは貴金属の付着方法は上
記に例示した方法に限られるものではなく、いかなる従
来法やそれらの組合わせによっても良い。It is desirable that the noble metal or alloy of the noble metal of the present invention is attached to both surfaces in contact with each other. The method of attaching the noble metal or the noble metal is not limited to the method exemplified above, but may be any conventional method or a combination thereof.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】[0032]
【表３】 [Table 3]
【００３３】[0033]
【表４】 [Table 4]
【００３４】[0034]
【実施例】以下、実施例により本発明をさらに詳しく説
明する。実際にステンレス鋼板をセパレータとして加工
し、市販の固体高分子膜に白金含有のカーボン微細粒ペ
ーストを塗布・乾燥させ、炭素繊維不織布をカレントコ
レクターとして燃料電池を作製した。The present invention will be described in more detail with reference to the following examples. Actually, a stainless steel sheet was processed as a separator, and a platinum-containing carbon fine particle paste was applied to a commercially available solid polymer film and dried, and a fuel cell was manufactured using a carbon fiber nonwoven fabric as a current collector.
【００３５】燃料ガスとして水素極側に純水素あるいは
模擬メタノール分解ガス（２５％ＣＯ2 、７５％Ｈ2 ）
を、酸素極側には模擬空気ガス（２０％Ｏ2 、８０％Ｎ
2 ）を大気圧で供給し、電池全体を９０℃になるよう高
温チャンバー内に保持し、正極から負極に向けて外部に
流れる短絡電流を測定することで、燃料電池性能の確認
試験を行った。この試験に用いた電極部のサイズは１０
０×１００mmであり、セパレータは耐食性を考慮し、板
厚０．４mmのＹＵＳ２７０ステンレス鋼板をプレス成形
によりガス流路や冷却水流路となる溝や穴を加工したも
のを用いた。Pure hydrogen or simulated methanol decomposition gas (25% CO 2 , 75% H 2 ) is placed on the hydrogen electrode side as a fuel gas.
Simulated air gas (20% O 2 , 80% N
2 ) was supplied at atmospheric pressure, the whole cell was kept in a high-temperature chamber at 90 ° C., and a short-circuit current flowing from the positive electrode to the negative electrode was measured. . The size of the electrode part used in this test was 10
The separator used was a YUS270 stainless steel plate having a thickness of 0.4 mm and press-formed to form grooves and holes serving as gas passages and cooling water passages in consideration of corrosion resistance.
【００３６】ステンレス鋼製セパレータの接触面とし
て、表１の結果を参考に０．５％塩化白金酸カリウムを
含む１Ｎ塩酸中で＃３２０シリコンカーバイド紙を用い
て軽く研摩した後、５分間のカソード電解処理を行って
白金を析出させたものと、比較のため無処理のものを用
意した。また、カーボンペーパーの接触面としては、イ
オン蒸着により約１０００ｎｍの金を付着させたもの
と、比較のための無処理のものを用意した。The contact surface of the stainless steel separator was lightly polished with # 320 silicon carbide paper in 1N hydrochloric acid containing 0.5% potassium chloroplatinate with reference to the results in Table 1, and then the cathode was treated for 5 minutes. An electrolytic treatment was performed to deposit platinum, and an untreated treatment was prepared for comparison. As the contact surface of the carbon paper, one having about 1000 nm of gold adhered by ion vapor deposition and one having no treatment for comparison were prepared.
【００３７】その結果、無処理の固体高分子型燃料電池
では約１５Ａしか発生しなかったのに対し、本発明によ
る接触抵抗低減処理をした固体高分子型燃料電池では、
短絡電流値は約８５Ａ発生し、内部の接触抵抗低減が大
幅な電力効率の向上を達成したことが判明した。As a result, only about 15 A was generated in the untreated solid polymer fuel cell, whereas in the solid polymer fuel cell treated with the contact resistance reducing treatment according to the present invention,
A short-circuit current value of about 85 A was generated, and it was found that a reduction in internal contact resistance achieved a significant improvement in power efficiency.
【００３８】[0038]
【発明の効果】上記のように本発明によれば、自動車内
燃機関や可搬型発電器として有望視されている固体高分
子型燃料電池のセパレータなどの材料として、これまで
の炭素材料に比べ低コストでコンパクト化が可能なステ
ンレス材料の適用にあたり、問題であった部材の接触抵
抗を大幅に低減でき、固体高分子型燃料電池の実用化に
大きく寄与するものである。As described above, according to the present invention, as a material for a separator of a polymer electrolyte fuel cell, which is considered to be promising as an automobile internal combustion engine or a portable power generator, a material lower than conventional carbon materials is used. When a stainless steel material that can be made compact at low cost is applied, the contact resistance of the member, which has been a problem, can be greatly reduced, which greatly contributes to the practical use of a polymer electrolyte fuel cell.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 菊池 正夫 富津市新富20−１ 新日本製鐵株式会社技 術開発本部内 Ｆターム(参考） 5H026 AA06 CX09 EE02 EE08 HH03 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masao Kikuchi 20-1 Shintomi, Futtsu Nippon Steel Corporation Technology Development Division F term (reference) 5H026 AA06 CX09 EE02 EE08 HH03
Claims (9)
に、貴金属または貴金属の合金が付着されていることを
特徴とする固体高分子型燃料電池部材用低接触抵抗ステ
ンレス鋼。1. A low contact resistance stainless steel for a polymer electrolyte fuel cell member, wherein a noble metal or an alloy of a noble metal is adhered to a portion which comes into contact with another member and generates a contact resistance.
または貴金属の合金が付着されていることを特徴とする
請求項１に記載の固体高分子型燃料電池部材用低接触抵
抗ステンレス鋼。2. The low contact resistance stainless steel for a polymer electrolyte fuel cell member according to claim 1, wherein a noble metal or a noble metal alloy is adhered after removing the oxide film on the surface.
が、５ｎｍ以上であることを特徴とする請求項１または
２に記載の固体高分子型燃料電池部材用低接触抵抗ステ
ンレス鋼。3. The low contact resistance stainless steel for a polymer electrolyte fuel cell member according to claim 1, wherein the noble metal or an alloy of the noble metal has an average thickness of 5 nm or more.
に、貴金属または貴金属の合金が付着されていることを
特徴とする固体高分子型燃料電池部材用低接触抵抗チタ
ン。4. A low contact resistance titanium for a polymer electrolyte fuel cell member, wherein a noble metal or an alloy of a noble metal is adhered to a portion which comes into contact with another member and generates contact resistance.
または貴金属の合金が付着されていることを特徴とする
請求項４に記載の固体高分子型燃料電池部材用低接触抵
抗チタン。5. The low contact resistance titanium for a polymer electrolyte fuel cell member according to claim 4, wherein a noble metal or a noble metal alloy is adhered after removing the oxide film on the surface.
が、５ｎｍ以上であることを特徴とする請求項４または
５に記載の固体高分子型燃料電池部材用低接触抵抗チタ
ン。6. The low contact resistance titanium for a polymer electrolyte fuel cell member according to claim 4, wherein the noble metal or an alloy of the noble metal has an average thickness of 5 nm or more.
に、貴金属または貴金属の合金が付着されていることを
特徴とする固体高分子型燃料電池部材用低接触抵抗炭素
材料。7. A low contact resistance carbon material for a polymer electrolyte fuel cell member, wherein a noble metal or an alloy of a noble metal is adhered to a portion which comes into contact with another member and generates contact resistance.
または貴金属の合金が付着されていることを特徴とする
請求項７に記載の固体高分子型燃料電池部材用低接触抵
抗炭素材料。8. The low contact resistance carbon material for a polymer electrolyte fuel cell member according to claim 7, wherein a noble metal or a noble metal alloy is adhered after removing the oxide film on the surface.
が、５ｎｍ以上であることを特徴とする請求項７または
８に記載の固体高分子型燃料電池部材用低接触抵抗炭素
材料。9. The low contact resistance carbon material for a polymer electrolyte fuel cell member according to claim 7, wherein the noble metal or an alloy of the noble metal has an average thickness of 5 nm or more.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17014299A JP5047408B2 (en) | 1999-06-16 | 1999-06-16 | Stainless steel or titanium separator for polymer electrolyte fuel cell |
| CA002300008A CA2300008C (en) | 1999-03-09 | 2000-03-06 | Stainless steel and titanium for solid polymer electrolyte fuel cell members |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17014299A JP5047408B2 (en) | 1999-06-16 | 1999-06-16 | Stainless steel or titanium separator for polymer electrolyte fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001006713A true JP2001006713A (en) | 2001-01-12 |
| JP5047408B2 JP5047408B2 (en) | 2012-10-10 |
Family
ID=15899458
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|---|---|---|---|
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| Country | Link |
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| JP (1) | JP5047408B2 (en) |
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