JPH04294063A - Highly anti-corrosive material for fuel cell with molten carbonate - Google Patents
Highly anti-corrosive material for fuel cell with molten carbonateInfo
- Publication number
- JPH04294063A JPH04294063A JP3057585A JP5758591A JPH04294063A JP H04294063 A JPH04294063 A JP H04294063A JP 3057585 A JP3057585 A JP 3057585A JP 5758591 A JP5758591 A JP 5758591A JP H04294063 A JPH04294063 A JP H04294063A
- Authority
- JP
- Japan
- Prior art keywords
- molten carbonate
- aluminum
- thin film
- corrosion
- vacuum
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 59
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 238000005260 corrosion Methods 0.000 claims abstract description 38
- 229910010199 LiAl Inorganic materials 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 230000007797 corrosion Effects 0.000 claims description 37
- 239000010409 thin film Substances 0.000 claims description 33
- 229910052782 aluminium Inorganic materials 0.000 abstract description 34
- 229910052744 lithium Inorganic materials 0.000 abstract description 21
- 150000002500 ions Chemical class 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 9
- 229910010092 LiAlO2 Inorganic materials 0.000 abstract description 8
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 4
- 238000001771 vacuum deposition Methods 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 18
- 229910001220 stainless steel Inorganic materials 0.000 description 18
- 238000001704 evaporation Methods 0.000 description 16
- 230000008020 evaporation Effects 0.000 description 16
- 229910021645 metal ion Inorganic materials 0.000 description 15
- 239000010408 film Substances 0.000 description 11
- 239000007769 metal material Substances 0.000 description 11
- 238000010891 electric arc Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910010981 Li2CO3—Na2CO3 Inorganic materials 0.000 description 1
- 101150000971 SUS3 gene Proteins 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- -1 is low Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
- Physical Vapour Deposition (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】この発明は、溶融炭酸塩燃料電池
に用いられ、高い耐腐食性を有する溶融炭酸塩燃料電池
用の高耐腐食性材料に関するものである。FIELD OF THE INVENTION This invention relates to highly corrosion resistant materials for use in molten carbonate fuel cells and having high corrosion resistance.
【０００２】0002
【従来の技術】従来から各種の燃料電池の開発研究が行
われている。その燃料電池の中で溶融炭酸塩燃料電池は
、電解質として用いる溶融した炭酸塩の電導度が水溶液
に比べて非常に大きいために大電流密度での動作が可能
で、第二世代燃料電池と呼ばれて大きな期待が持たれて
いる。BACKGROUND OF THE INVENTION Research and development on various types of fuel cells have been carried out. Among these fuel cells, molten carbonate fuel cells are capable of operating at high current densities because the conductivity of the molten carbonate used as an electrolyte is much higher than that of aqueous solutions, and are called second-generation fuel cells. There are high expectations.
【０００３】この溶融炭酸塩燃料電池の一例を図３に基
づいて説明する。図３は、溶融炭酸塩燃料電池の構造を
説明する概略図である。この溶融炭酸塩燃料電池は、６
５０℃の高温度で溶融状態にあるＬｉ２ＣＯ３−Ｎａ２
ＣＯ３系の溶融炭酸塩を含浸する電解質板４１の片面に
、酸化ニッケル（ＮｉＯ ）からなるカソード電極４２
，波形のセパレータ材４３およびニッケル（Ｎｉ）から
なるアノード電極４４を設け、電解質板４１の他面に、
ニッケル（Ｎｉ）からなるアノード電極４４，波形のセ
パレータ材４３および酸化ニッケル（ＮｉＯ ）からな
るカソード電極４２を設け、各セパレータ材４３の端部
と電解質板４１との間をシーリングするようにウエット
シール部材４５を設けたものである。なお、Ａは燃料ガ
ス、Ｂは酸化ガスである。An example of this molten carbonate fuel cell will be explained based on FIG. 3. FIG. 3 is a schematic diagram illustrating the structure of a molten carbonate fuel cell. This molten carbonate fuel cell has 6
Li2CO3-Na2 in a molten state at a high temperature of 50℃
A cathode electrode 42 made of nickel oxide (NiO 2 ) is placed on one side of an electrolyte plate 41 impregnated with CO3-based molten carbonate.
, a corrugated separator material 43 and an anode electrode 44 made of nickel (Ni) are provided, and on the other side of the electrolyte plate 41,
An anode electrode 44 made of nickel (Ni), a corrugated separator material 43, and a cathode electrode 42 made of nickel oxide (NiO 2 ) are provided, and a wet seal is applied to seal between the end of each separator material 43 and the electrolyte plate 41. A member 45 is provided. Note that A is a fuel gas and B is an oxidizing gas.
【０００４】このような構造の溶融炭酸塩燃料電池にお
いて、特に耐腐食性を必要とする部分のセパレータ材４
３，ウエットシール部材４５等には、ステンレスまたは
ステンレス系鋼材等の特殊金属材料，表面にアルミニウ
ム（Ａｌ）薄膜を真空蒸着法で設けたステンレスまたは
ステンレス系鋼材等の特殊金属材料，表面にアルミニウ
ム（Ａｌ）薄膜をイオンプレーディング法で設けて熱処
理したステンレスまたはステンレス系鋼材等の特殊金属
材料等が実用に供されている。[0004] In a molten carbonate fuel cell having such a structure, the separator material 4 is used in parts that particularly require corrosion resistance.
3. The wet seal member 45 etc. is made of a special metal material such as stainless steel or stainless steel, a special metal material such as stainless steel or stainless steel with a thin aluminum (Al) film coated on the surface by vacuum evaporation, or a special metal material such as aluminum (Al) on the surface. Special metal materials such as stainless steel or stainless steel materials in which a thin Al) film is provided by an ion plating method and then heat treated are in practical use.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、６５０
℃の高い温度状態にあるＬｉ２ＣＯ３−Ｎａ２ＣＯ３系
の溶融炭酸塩にさらされて使用されるセパレータ材４３
，ウエットシール部材４５に、耐腐食性を有するステン
レスまたはステンレス系鋼材等の特殊金属材料を用いて
も、溶融炭酸塩燃料電池が使用されている間は高温度（
６５０℃）のＬｉ２ＣＯ３−Ｎａ２ＣＯ３系の溶融炭酸
塩にさられるため、腐食が発生して溶融炭酸塩の液漏れ
が発生し、溶融炭酸塩燃料電池が使用できなくなる。[Problem to be solved by the invention] However, 650
Separator material 43 used by being exposed to Li2CO3-Na2CO3-based molten carbonate at a high temperature of ℃
, Even if a special metal material such as corrosion-resistant stainless steel or stainless steel is used for the wet seal member 45, high temperatures (
650° C.), corrosion occurs and the molten carbonate leaks, making the molten carbonate fuel cell unusable.
【０００６】また、表面にアルミニウム（Ａｌ）薄膜を
真空蒸着法で設けたステンレスまたはステンレス系鋼材
等の特殊金属材料をセパレータ材４３，ウエットシール
部材４５として用いた場合は、表面に蒸着したアルミニ
ウム（Ａｌ）と溶融炭酸塩のリチウム（Ｌｉ）とが反応
してアルミニウム（Ａｌ）を主成分とするＬｉＡｌＯ２
の不働態が形成され耐腐食性が向上するものの、真空蒸
着で設けられるアルミニウム（Ａｌ）薄膜にはピンホー
ルが存在するため、このピンホールから腐食（ピンホー
ル腐食）が発生するとともに、アルミニウム（Ａｌ）薄
膜と特殊金属材料との密着性が低いため熱応力でアルミ
ニウム（Ａｌ）薄膜が剥離し易く、構成材料の表面およ
び内部に腐食が発生し、溶融炭酸塩燃料電池が使用でき
なくなる。Furthermore, when a special metal material such as stainless steel or stainless steel material on which a thin aluminum (Al) film is formed on the surface by vacuum evaporation is used as the separator material 43 and the wet seal member 45, the aluminum (Al) deposited on the surface may be Al) and molten carbonate lithium (Li) react to form LiAlO2 whose main component is aluminum (Al).
Although the aluminum (Al) thin film formed by vacuum evaporation has pinholes, corrosion occurs from these pinholes (pinhole corrosion). Because the adhesion between the aluminum (Al) thin film and the special metal material is low, the aluminum (Al) thin film easily peels off due to thermal stress, corrosion occurs on the surface and inside of the constituent materials, and the molten carbonate fuel cell becomes unusable.
【０００７】さらに、表面にアルミニウム（Ａｌ）薄膜
をイオンプレーディング法で設けて熱処理したステンレ
スまたはステンレス系鋼材等の特殊金属材料セパレータ
材４３，ウエットシール部材４５として用いた場合は、
アルミニウム（Ａｌ）薄膜のピンホールをなくしピンホ
ール腐食を防止することができるが、アルミニウム（Ａ
ｌ）薄膜を形成するための条件の一つである真空度が低
いため不純物が混入して局部腐食が発生し易く、腐食に
伴う欠陥部の形成により、溶融炭酸塩燃料電池が使用で
きなくなる。また、アルミニウム（Ａｌ）薄膜の形成と
高温度の熱処理とを行うため、特殊金属材料の材質が限
定されたり、生産性が悪く製造コストが高くなるという
欠点がある。Furthermore, when a special metal material such as stainless steel or stainless steel which has been heat-treated with an aluminum (Al) thin film formed on the surface by ion plating is used as the separator material 43 and the wet seal member 45,
Pinholes in aluminum (Al) thin films can be eliminated and pinhole corrosion can be prevented;
l) Since the degree of vacuum, which is one of the conditions for forming a thin film, is low, impurities are mixed in and local corrosion is likely to occur, and the formation of defects due to corrosion makes the molten carbonate fuel cell unusable. Furthermore, since the formation of an aluminum (Al) thin film and high-temperature heat treatment are performed, there are disadvantages in that the quality of the special metal material is limited, and productivity is poor and manufacturing costs are high.
【０００８】この発明の目的は、高温度の溶融炭酸塩に
長時間さらされて使用した場合でも高い耐腐食特性を示
す溶融炭酸塩燃料電池用の高耐腐食性材料を提供するこ
とである。It is an object of the present invention to provide a highly corrosion resistant material for molten carbonate fuel cells that exhibits high corrosion resistance properties even when used with prolonged exposure to high temperature molten carbonates.
【０００９】[0009]
【課題を解決するための手段】この発明の溶融炭酸塩燃
料電池用の高耐腐食性材料は、基材の表面にＬｉＡｌ合
金薄膜またはＬｉＡｌＯ２薄膜を設けたものである。[Means for Solving the Problems] The highly corrosion-resistant material for molten carbonate fuel cells of the present invention is one in which a LiAl alloy thin film or a LiAlO2 thin film is provided on the surface of a base material.
【００１０】0010
【作用】この発明の溶融炭酸塩燃料電池用の高耐腐食性
材料は、基材の表面に設けたＬｉＡｌ合金薄膜またはＬ
ｉＡｌＯ２薄膜が、通常の金属の状態よりも貴金属性を
おびた状態である不働態（ｐａｓｓｉｖｉｔｙ または
ｐａｓｓｉｖｅ ｓｔａｔｅ）として作用するので、溶
融状態にある炭酸塩に対して高い耐腐食性を示す。[Operation] The highly corrosion-resistant material for molten carbonate fuel cells of the present invention is a LiAl alloy thin film or L
Since the iAlO2 thin film acts as a passivity or passive state, which is more noble than the normal metal state, it exhibits high corrosion resistance to carbonates in the molten state.
【００１１】[0011]
【実施例】この発明の溶融炭酸塩燃料電池用の高耐腐食
性材料の第１の実施例を図１に基づいて説明する。図１
は、ＩＶＤ法（Ｉｏｎ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉ
ｏｎ法）により基材の表面に各種薄膜を形成する装置の
概略構成図である。EXAMPLE A first example of the highly corrosion-resistant material for a molten carbonate fuel cell according to the present invention will be described with reference to FIG. Figure 1
is the IVD method (Ion Vapor Deposit
1 is a schematic configuration diagram of an apparatus for forming various thin films on the surface of a base material by the on method.
【００１２】この装置は、真空装置内（図示せず）にお
いて、水を循環することにより水冷できるホルダ１１に
基材１２が固定されている。この基材１２に対向する位
置には二つの蒸発源１３，２３とイオン源１５とが配置
されている。この蒸発源１３，２３は、電子ビーム，レ
ーザ線または高周波等により高温度に加熱することがで
きるもので、蒸発源１３の中にはリチウム（Ｌｉ）から
なる蒸発物質１４が、また蒸発源２３の中にはアルミニ
ウム（Ａｌ）からなる蒸発物質２４が入れられる。In this device, a base material 12 is fixed to a holder 11 that can be water-cooled by circulating water in a vacuum device (not shown). Two evaporation sources 13 and 23 and an ion source 15 are arranged at positions facing the base material 12. The evaporation sources 13 and 23 can be heated to a high temperature by an electron beam, laser beam, high frequency, etc. Inside the evaporation source 13 is an evaporation substance 14 made of lithium (Li); An evaporative substance 24 made of aluminum (Al) is placed inside.
【００１３】また、イオン源１５は、カウフマン型やプ
ラズマを閉じ込めるためのカスプ磁場を用いたバケット
型等のもので、少なくとも１種類以上の不活性ガスまた
は酸素ガス（Ｏ２）が供給され、これらのガスをイオン
化してイオン１６として基材１２の表面に照射する装置
である。さらに、真空装置内には、膜厚計１７と電流測
定計１８が配置されている。この膜厚計１７は、基材１
２の表面に蒸着されるリチウム（Ｌｉ）およびアルミニ
ウム（Ａｌ）の粒子数ならびに膜厚を計測するためのも
のであり、例えば水晶振動子を使用した振動型膜厚計等
である。また、電流測定計１８は、基材１２に照射され
る不活性ガスまたは酸素ガス（Ｏ２）のイオン１６の量
を計測するためのものであり、例えばファラデーカップ
のような２次電子抑制電極をもつカップ型構造のイオン
ビーム電流測定計等である。The ion source 15 is of the Kaufmann type or a bucket type using a cusp magnetic field for confining plasma, and is supplied with at least one type of inert gas or oxygen gas (O2). This is a device that ionizes gas and irradiates the surface of the base material 12 as ions 16. Furthermore, a film thickness meter 17 and a current measuring meter 18 are arranged within the vacuum apparatus. This film thickness meter 17 measures the thickness of the base material 1.
This device is used to measure the number of particles and film thickness of lithium (Li) and aluminum (Al) deposited on the surface of the film 2, and is, for example, a vibrating film thickness meter using a crystal oscillator. Further, the current measuring meter 18 is used to measure the amount of ions 16 of an inert gas or oxygen gas (O2) irradiated onto the base material 12, and is used to measure the amount of ions 16 of an inert gas or oxygen gas (O2) irradiated onto the base material 12. This is an ion beam current measuring meter with a cup-shaped structure.
【００１４】なお、イオン源１５に供給されてイオン１
６として基材１２に照射する不活性ガスとしては、ヘリ
ウム（Ｈｅ），ネオン（Ｎｅ），アルゴン（Ａｒ），ク
リプトン（Ｋｒ），キセノン（Ｘｅ）の少なくとも１種
類以上からなるなるものである。このような構成の装置
において、ステンレス材（ＳＵＳ３１６ ）からなる基
材１２をホルダ１１に固定した後、リチウム（Ｌｉ）と
アルミニウム（Ａｌ）とを蒸発物質１４，２４として蒸
発源１３，２３に配置して真空装置の内部を５×１０−
６〔Ｔｏｒｒ〕以下の高真空に保持する。そして、蒸発
源１３，２３を電子ビームで加熱して蒸発物質１４，２
４を基材１２の表面に真空蒸着すると同時に、酸素ガス
（Ｏ２）をイオン源１５に供給してイオン１６として２
０ ＫｅＶ の照射エネルギーで照射し、基材１２の
表面に蒸発物質１４，２４すなわちリチウム（Ｌｉ），
アルミニウム（Ａｌ）と酸素（Ｏ）との混合物からなる
ＬｉＡｌＯ２薄膜を厚さ５〔μｍ〕形成して高耐腐食性
材料としたものである。Note that ions 1 are supplied to the ion source 15.
The inert gas 6 irradiated onto the base material 12 is made of at least one of helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe). In an apparatus having such a configuration, after fixing the base material 12 made of stainless steel material (SUS316) to the holder 11, lithium (Li) and aluminum (Al) are placed as evaporation substances 14 and 24 in the evaporation sources 13 and 23. and the inside of the vacuum device to 5×10−
Maintain a high vacuum of 6 Torr or less. Then, the evaporation sources 13 and 23 are heated with an electron beam to form the evaporation substances 14 and 2.
At the same time, oxygen gas (O2) is supplied to the ion source 15 to produce 2 as ions 16.
Irradiation is performed with an irradiation energy of 0 KeV to form evaporated substances 14, 24, ie, lithium (Li), on the surface of the base material 12.
A LiAlO2 thin film made of a mixture of aluminum (Al) and oxygen (O) was formed to a thickness of 5 [μm] to provide a highly corrosion-resistant material.
【００１５】このとき、蒸発源１３，２３の加熱温度を
調節することにより、各蒸発物質１４，２４すなわちリ
チウム（Ｌｉ）とアルミニウム（Ａｌ）との蒸発量を適
宜調整することができる。なお、ＬｉＡｌＯ２薄膜の形
成中は、膜厚計１７および電流測定計１８により、基材
１２に到達するリチウム（Ｌｉ）またはアルミニウム（
Ａｌ）からなる蒸発物質１４，２４の粒子数とイオン１
６の粒子数とを常時測定・監視するとともに、その値が
所定の値にコントロールされる。At this time, by adjusting the heating temperature of the evaporation sources 13 and 23, the amount of evaporation of each evaporation substance 14 and 24, that is, lithium (Li) and aluminum (Al), can be adjusted as appropriate. During the formation of the LiAlO2 thin film, the thickness meter 17 and current meter 18 measure the amount of lithium (Li) or aluminum (
Number of particles and ions 1 of evaporated substances 14 and 24 consisting of Al)
The number of particles of 6 is constantly measured and monitored, and the value is controlled to a predetermined value.
【００１６】さらに、この第１の実施例では、二つ設け
た蒸発源１３，２３にリチウム（Ｌｉ）およびアルミニ
ウム（Ａｌ）からなる蒸発物質１４，２４を配置させ、
各蒸発物質１４，２４を個別に真空蒸着する例を説明し
たが、一つの蒸発源１３の中に所定の比率で作られたリ
チウム−アルミニウム合金（Ｌｉ−Ａｌ 合金）を配置
させて真空蒸着するようにしてもよい。Furthermore, in this first embodiment, evaporation substances 14 and 24 made of lithium (Li) and aluminum (Al) are arranged in two evaporation sources 13 and 23,
Although an example has been described in which the evaporation substances 14 and 24 are individually vacuum evaporated, a lithium-aluminum alloy (Li-Al alloy) made at a predetermined ratio is placed in one evaporation source 13 and vacuum evaporated. You can do it like this.
【００１７】なお、イオン源１５に供給する酸素ガス（
Ｏ２）をアルゴン等の不活性ガスに置換すると、ＬｉＡ
ｌＯ２薄膜に換えてＬｉＡｌ合金薄膜を形成することが
できる。つぎに、溶融炭酸塩燃料電池用の高耐腐食性材
料の第２の実施例を図２に基づいて説明する。図２は、
真空アーク放電蒸着法により基材の表面に各種薄膜を形
成する真空アーク放電型蒸着装置と呼ばれている装置の
概略構成図である。Note that the oxygen gas (
When O2) is replaced with an inert gas such as argon, LiA
A LiAl alloy thin film can be formed instead of the lO2 thin film. Next, a second example of a highly corrosion-resistant material for a molten carbonate fuel cell will be described with reference to FIG. Figure 2 shows
1 is a schematic configuration diagram of an apparatus called a vacuum arc discharge type deposition apparatus that forms various thin films on the surface of a base material by a vacuum arc discharge deposition method.
【００１８】この真空アーク放電型蒸着装置は、各種ガ
スを導入するガス導入部１ａと真空ポンプ（図示せず）
を接続する真空排気部１ｂとを設けた真空装置１の内部
の一方にリチウム（Ｌｉ）とアルミニウム（Ａｌ）とか
らなる二つの電極２，３２を設け、内部の他方にホルダ
３を設けて表面を電極２，３２に対向するようにして基
材４を支持配置する。This vacuum arc discharge type vapor deposition apparatus includes a gas introduction section 1a for introducing various gases and a vacuum pump (not shown).
Two electrodes 2 and 32 made of lithium (Li) and aluminum (Al) are provided on one side of the vacuum device 1, which is provided with a vacuum evacuation section 1b that connects the The base material 4 is supported and arranged so as to face the electrodes 2 and 32.
【００１９】そして、真空装置１が陽極となり各電極２
，３２が陰極となるように、トリガー５ａ，３５ｂを有
するアーク電源５，３５が接続され、真空装置１と電極
２との間に直流電圧を印加できるようにするとともに、
基材４にはホルダ３を介して負のバイアス電圧を印加す
るバイアス電源６が接続されている。このような構成の
真空アーク放電型蒸着装置において、真空装置１の真空
排気部１ｂから真空ポンプ（図示せず）で排気して真空
装置１の内部を５×１０−６〔Ｔｏｒｒ〕に保持した後
、ガス導入部１ａよりＡｒからなる不活性ガスを１〔ｍ
Ｔｏｒｒ 〕導入した後、アーク電源５，３５で真空装
置１と電極２，３２との間に５０〔Ａ〕のアーク電流を
流してアーク放電させ、各電極２，３２の金属すなわち
リチウム（Ｌｉ）およびアルミニウム（Ａｌ）の金属イ
オンＭおよび金属イオンＭ′と電子ｅとのプラズマを発
生させる。Then, the vacuum device 1 becomes an anode, and each electrode 2
, 32 serve as cathodes, the arc power sources 5 and 35 having triggers 5a and 35b are connected so that a DC voltage can be applied between the vacuum device 1 and the electrode 2, and
A bias power supply 6 that applies a negative bias voltage is connected to the base material 4 via the holder 3 . In the vacuum arc discharge type deposition apparatus having such a configuration, the inside of the vacuum apparatus 1 was maintained at 5×10-6 [Torr] by evacuating the vacuum pump (not shown) from the evacuation part 1b of the vacuum apparatus 1. After that, inert gas consisting of Ar is supplied from the gas introduction part 1a to 1 [m].
[Torr] After the introduction, an arc current of 50 [A] is caused to flow between the vacuum device 1 and the electrodes 2, 32 using the arc power supplies 5, 35 to cause arc discharge, and the metal of each electrode 2, 32, that is, lithium (Li) Then, a plasma of aluminum (Al) metal ions M and metal ions M' and electrons e is generated.
【００２０】そして、真空装置１よりも負の１００〔Ｖ
〕のバイアス電圧をホルダ３を介してバイアス電源６で
基材４に印加し、リチウム（Ｌｉ）の金属イオンＭとア
ルミニウム（Ａｌ）のプラズマの金属イオンＭ′とを基
材４に向けて加速し、基材４の表面にリチウム（Ｌｉ）
の金属イオンＭとアルミニウム（Ａｌ）の金属イオンＭ
′とを付着させ、リチウム（Ｌｉ）とアルミニウム（Ａ
ｌ）とからなるＬｉＡｌ合金薄膜を厚さ５〔μｍ〕形成
して高耐腐食性材料としたものである。[0020] Then, 100 [V] which is more negative than the vacuum device 1
] is applied to the base material 4 by the bias power supply 6 via the holder 3, and lithium (Li) metal ions M and aluminum (Al) plasma metal ions M' are accelerated toward the base material 4. lithium (Li) on the surface of the base material 4.
metal ion M and aluminum (Al) metal ion M
', lithium (Li) and aluminum (A
A highly corrosion-resistant material is obtained by forming a LiAl alloy thin film consisting of (1) to a thickness of 5 [μm].
【００２１】このとき、各アーク電源５，３５によるア
ーク電流やバイアス電圧を調節することにより、リチウ
ム（Ｌｉ）の金属イオンＭとアルミニウム（Ａｌ）の金
属イオンＭ′との発生量すなわち各電極２，３２の蒸発
量を適宜調整することができ、形成されるＬｉＡｌ合金
薄膜のリチウム（Ｌｉ）とアルミニウム（Ａｌ）との比
率を変更することができる。At this time, by adjusting the arc current and bias voltage of each arc power source 5, 35, the amount of lithium (Li) metal ions M and aluminum (Al) metal ions M' generated, that is, the amount of each electrode 2 , 32 can be adjusted as appropriate, and the ratio of lithium (Li) to aluminum (Al) in the formed LiAl alloy thin film can be changed.
【００２２】なお、この第２の実施例では、リチウム（
Ｌｉ）およびアルミニウム（Ａｌ）からなる二つの電極
２，３２とアーク電源５，３５とを設け、電極２のリチ
ウム（Ｌｉ）の金属イオンＭと電極３２のアルミニウム
（Ａｌ）の金属イオンＭ′とを個別に真空アーク放電蒸
着する例を説明したが、所定の比率で作られたリチウム
−アルミニウム合金（Ｌｉ−Ａｌ 合金）からなる電極
２のみを配置し、アーク放電によりリチウム（Ｌｉ）の
金属イオンＭとアルミニウム（Ａｌ）の金属イオンＭ′
とを同時に発生させ、リチウム（Ｌｉ）とアルミニウム
（Ａｌ）とからなるＬｉＡｌ合金薄膜を形成してもよい
。Note that in this second embodiment, lithium (
Two electrodes 2, 32 made of Li) and aluminum (Al) and an arc power source 5, 35 are provided, and metal ions M of lithium (Li) in the electrode 2 and metal ions M' of aluminum (Al) in the electrode 32 are provided. Although we have explained an example in which lithium (Li) metal ions are individually deposited by vacuum arc discharge, only the electrode 2 made of lithium-aluminum alloy (Li-Al alloy) made at a predetermined ratio is arranged, and lithium (Li) metal ions are deposited by arc discharge. M and aluminum (Al) metal ion M'
may be generated simultaneously to form a LiAl alloy thin film consisting of lithium (Li) and aluminum (Al).
【００２３】このようにして得られた各実施例と、従来
から耐腐食性金属材料として用いられているステンレス
材（ＳＵＳ３１６Ｌ），真空蒸着法により表面にアルミ
ニウム（Ａｌ）薄膜を形成したステンレス材（ＳＵＳ３
１６Ｌ）とを、「ステンレス鋼のアノード分極曲線測定
方法（ＪＩＳ Ｇ ０５７９（１９８３））」によ
り腐食試験を行い、自然電位値（Ｅｃｏｒｒ）と活性化
速度値（自然電位値（Ｅｃｏｒｒ）から活性電位（Ｅａ
ｃｔ．）に達するまでの腐食速度）とを測定するととも
に、腐食試験後の各構成材料の断面観察と断面の組成分
析とを走査型電子顕微鏡（ＳＥＭ）と波長分散型Ｘ線分
析装置とにより行った。[0023] Examples obtained in this manner, stainless steel material (SUS316L) conventionally used as a corrosion-resistant metal material, and stainless steel material (SUS316L) with a thin aluminum (Al) film formed on the surface by vacuum evaporation method. SUS3
16L) was subjected to a corrosion test according to the "Method for Measuring Stainless Steel Anode Polarization Curves (JIS G 0579 (1983))", and the activation potential was determined from the natural potential value (Ecorr) and activation rate value (self-potential value (Ecorr)). (Ea
ct. In addition to measuring the corrosion rate until the corrosion rate reached .
【００２４】その結果、従来から耐腐食性金属して用い
られているステンレス材（ＳＵＳ３１６Ｌ），真空蒸着
法により表面にアルミニウム（Ａｌ）薄膜を形成したス
テンレス材（ＳＵＳ３１６Ｌ）に比べて、実施例は自然
電位値（Ｅｃｏｒｒ）が高く、活性化速度も遅いことか
ら耐腐食性に優れていることが確認された。また、腐食
試験後の各構成材料の断面観察および断面の組成分析で
は、各実施例は、表面に形成したＬｉＡｌ合金薄膜およ
びＬｉＡｌＯ２薄膜で腐食の進行が止まっているの対し
、従来の耐腐食性材料は基材内部の奥深くまで腐食が進
行していた。As a result, compared to the stainless steel material (SUS316L) conventionally used as a corrosion-resistant metal, and the stainless steel material (SUS316L) on which a thin aluminum (Al) film was formed on the surface by vacuum evaporation, the embodiment It was confirmed that the material has excellent corrosion resistance because of its high self-potential value (Ecorr) and slow activation rate. In addition, cross-sectional observation and cross-sectional composition analysis of each constituent material after the corrosion test revealed that in each example, the progress of corrosion was stopped by the LiAl alloy thin film and LiAlO2 thin film formed on the surface, whereas the conventional corrosion resistance Corrosion had progressed deep into the base material.
【００２５】さらに、各実施例について不働態が破壊す
るまでの電力消費量を測定した結果、電力消費量がすべ
て高い値を示し、不働態の強度が高いことが確認された
。以上のように、各方法により基材１２，４の表面に設
けたＬｉＡｌ合金薄膜またはＬｉＡｌＯ２薄膜が、通常
の金属の状態よりも貴金属性をおびた状態である不働態
（ｐａｓｓｉｖｉｔｙ またはｐａｓｓｉｖｅ ｓｔａ
ｔｅ）として作用することにより、基材１２，４の表面
で局部電池の作用による腐食電流を流れ難くするので、
高温度の溶融炭酸塩に長時間さらされて使用しても高い
耐腐食特性を示すことが分かる。Furthermore, as a result of measuring the power consumption until the passive state was destroyed for each of the examples, it was confirmed that the power consumption was all high, and the strength of the passive state was high. As described above, the LiAl alloy thin film or LiAlO2 thin film provided on the surfaces of the base materials 12 and 4 by each method is in a passive state, which is a state with more noble metal properties than the normal metal state.
te), it makes it difficult for corrosion current to flow due to the action of local batteries on the surfaces of the base materials 12 and 4.
It can be seen that it exhibits high corrosion resistance even after being exposed to high-temperature molten carbonate for a long time.
【００２６】なお、ＩＶＤ法（Ｉｏｎ Ｖａｐｏｒ Ｄ
ｅｐｏｓｉｔｉｏｎ法）により高耐腐食性材料の薄膜を
形成する装置（図１）および真空アーク放電型蒸着装置
（図２）は、低温度かつ高真空度の条件でＬｉＡｌＯ２
薄膜およびＬｉＡｌ合金薄膜を形成することができるの
で、基材１２，４の材質が限定されることもなく、不純
物の混入も避けることができる。[0026] Furthermore, the IVD method (Ion Vapor D
The equipment (Fig. 1) that forms thin films of highly corrosion-resistant materials by the deposition method (Fig.
Since a thin film and a LiAl alloy thin film can be formed, the materials of the base materials 12 and 4 are not limited, and contamination with impurities can be avoided.
【００２７】特に、真空アーク放電型蒸着装置（図２）
は、ＬｉＡｌ合金薄膜を形成させるために必要な時間が
短く、かつ金属材料の電極を蒸発源として用いるので、
複数の電極を用いて金属薄膜の形成を行うことができ、
複雑な形状や表面積の大きい基材４にも対応することが
でき、生産性をより一層高めることが可能である。In particular, vacuum arc discharge type deposition equipment (FIG. 2)
Since the time required to form a LiAl alloy thin film is short and a metal material electrode is used as an evaporation source,
A thin metal film can be formed using multiple electrodes,
It is possible to handle base materials 4 with complex shapes and large surface areas, and it is possible to further improve productivity.
【００２８】[0028]
【発明の効果】この発明の溶融炭酸塩燃料電池用の高耐
腐食性材料は、基材の表面に設けたＬｉＡｌ合金薄膜ま
たはＬｉＡｌＯ２薄膜が、通常の金属の状態よりも貴金
属性をおびた状態である不働態（ｐａｓｓｉｖｉｔｙま
たはｐａｓｓｉｖｅ ｓｔａｔｅ）として作用すること
により、基材の表面で局部電池の作用による腐食電流を
流れ難くするので、高温度の溶融炭酸塩に長時間さらさ
れて使用しても高い耐腐食特性を示す。Effects of the Invention The highly corrosion-resistant material for molten carbonate fuel cells of the present invention has a state in which the LiAl alloy thin film or LiAlO2 thin film provided on the surface of the base material has more noble metal properties than the normal metal state. By acting as a passivity or passive state, it makes it difficult for corrosion current due to the action of local batteries to flow on the surface of the base material, so it can be used even if exposed to high temperature molten carbonate for a long time. Shows high corrosion resistance properties.
【図１】ＩＶＤ法により薄膜を形成する装置の概略構成
図である。FIG. 1 is a schematic diagram of an apparatus for forming a thin film by an IVD method.
【図２】真空アーク放電型蒸着装置の概略構成図である
。FIG. 2 is a schematic configuration diagram of a vacuum arc discharge type deposition apparatus.
【図３】溶融炭酸塩燃料電池の構造を説明する概略図で
ある。FIG. 3 is a schematic diagram illustrating the structure of a molten carbonate fuel cell.
１ 真空装置
２，３２ 電極
４ 基材
５，３５ アーク電源
６ バイアス電源
Ｍ リチウム（Ｌｉ）の金属イオン
Ｍ′ アルミニウム（Ａｌ）の金属イオ
ンｅ 電子
１２ 基材
１４，２４ 蒸発物質
１６ イオン1 Vacuum device 2, 32 Electrode 4 Base material 5, 35 Arc power source 6 Bias power source M Lithium (Li) metal ion M' Aluminum (Al) metal ion e Electron 12 Base material 14, 24 Evaporated substance 16 Ion
Claims (1)
ＡｌＯ２薄膜を設けた溶融炭酸塩燃料電池用の高耐腐食
性材料。Claim 1: LiAl alloy thin film or Li
Highly corrosion resistant material for molten carbonate fuel cells with AlO2 thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3057585A JPH04294063A (en) | 1991-03-22 | 1991-03-22 | Highly anti-corrosive material for fuel cell with molten carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3057585A JPH04294063A (en) | 1991-03-22 | 1991-03-22 | Highly anti-corrosive material for fuel cell with molten carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04294063A true JPH04294063A (en) | 1992-10-19 |
Family
ID=13059927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3057585A Pending JPH04294063A (en) | 1991-03-22 | 1991-03-22 | Highly anti-corrosive material for fuel cell with molten carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04294063A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999028522A1 (en) * | 1997-12-02 | 1999-06-10 | Korea Research Institute Of Chemical Technology | PROCESS FOR PREPARING A LiMO2 TYPE HETEROMETALLIC OXIDE FILM |
| WO2008102663A1 (en) * | 2007-02-22 | 2008-08-28 | Mitsubishi Heavy Industries, Ltd. | Surface film member, process for rpoducing the surface covering member, cutting tool, and machine tool |
-
1991
- 1991-03-22 JP JP3057585A patent/JPH04294063A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999028522A1 (en) * | 1997-12-02 | 1999-06-10 | Korea Research Institute Of Chemical Technology | PROCESS FOR PREPARING A LiMO2 TYPE HETEROMETALLIC OXIDE FILM |
| WO2008102663A1 (en) * | 2007-02-22 | 2008-08-28 | Mitsubishi Heavy Industries, Ltd. | Surface film member, process for rpoducing the surface covering member, cutting tool, and machine tool |
| JP4950276B2 (en) * | 2007-02-22 | 2012-06-13 | 三菱重工業株式会社 | Surface coating member, manufacturing method thereof, cutting tool and machine tool |
| US8288019B2 (en) | 2007-02-22 | 2012-10-16 | Mitsubishi Heavy Industries, Ltd. | Surface coating film, method of manufacturing thereof, cutting tool and machine tool |
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