WO2005056858A1 - Alliage amorphe - Google Patents

Alliage amorphe Download PDF

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Publication number
WO2005056858A1
WO2005056858A1 PCT/JP2004/018547 JP2004018547W WO2005056858A1 WO 2005056858 A1 WO2005056858 A1 WO 2005056858A1 JP 2004018547 W JP2004018547 W JP 2004018547W WO 2005056858 A1 WO2005056858 A1 WO 2005056858A1
Authority
WO
WIPO (PCT)
Prior art keywords
separator
metallic glass
glass alloy
alloy
corrosion resistance
Prior art date
Application number
PCT/JP2004/018547
Other languages
English (en)
Japanese (ja)
Inventor
Akihisa Inoue
Zhang Wei
Hideki Onishi
Original Assignee
Dynax Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dynax Corporation filed Critical Dynax Corporation
Publication of WO2005056858A1 publication Critical patent/WO2005056858A1/fr

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Classifications

    • 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
    • H01M8/0208—Alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/001—Amorphous alloys with Cu as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention belongs to the technical field of metallic glass alloys, and more specifically, to the technical field of metallic glass alloys for separators used as materials for separators incorporated in cells of polymer electrolyte fuel cells. Background art
  • a polymer electrolyte fuel cell (hereinafter referred to as a “fuel cell”) is a device that generates electricity by supplying a reaction gas (hydrogen and oxygen) to an electrode composed of a polymer electrolyte membrane.
  • FIG. 2 is a perspective view of a cell C which is a minimum unit constituting the fuel cell.
  • the cell C of the fuel cell includes two electrodes E 1 and E 2 (anode and force sword) composed of a catalyst layer and a porous support layer, an electrolyte D inserted between the electrodes El and E 2, and an electrode E 1 ⁇ Separator 1100 placed outside E2.
  • a voltage of slightly less than 1 V can be obtained for each cell. Therefore, as an actual fuel cell, a cell in which several tens to several hundreds of cells C are stacked in series is usually used.
  • FIG. 3 is a front view of a conventional separator 100 used for a fuel cell. As shown in FIG. 3, a large number of grooves 120 having a width and a depth of about 0.5 to 2 mm are provided on both sides of the plate-like separator 100 as shown in FIG. 20 functions as a flow path for the reaction gas and a discharge path for water generated by the reaction.
  • the above separator 100 serves not only as a partition plate between the cells C but also as an electrode E 1 (or a neighboring electrode) via a groove 120. It is provided to supply reaction gas to E 2) and to discharge water generated by the reaction to the outside.
  • Separation 100 also plays a role in transmitting the electricity generated in cell C to the outside.
  • electrodes El and E2 anode side, (Gas side)
  • the gas shielding property is high so that the reaction gas supplied to the reaction gas does not mix, and it is excellent in corrosion resistance and oxidation resistance so that it is not corroded by the reaction gas, lightweight, and conductive. Further, it is required to have a strength capable of withstanding the load of each stacked cell C and to have a groove depth of about 1 mm.
  • isotropic carbon has been used as the material of Separation 100 that satisfies the above characteristics.
  • the mechanical strength and formability were limited when the separator was thinner. Therefore, at present, the development of metal-based separators that are excellent in mechanical strength and formability even when the separators are made thinner is underway.
  • the first is the low corrosion resistance due to the properties of metals.
  • water is present during the reaction of the fuel cell, but the metal is easily corroded in such an atmosphere containing water, and when the metal corrodes, metal ions are formed in the generated water.
  • the catalyst becomes inactive due to contamination.
  • the second point is the high contact resistance (low conductivity) derived from the properties of metals. Since a passivation layer is formed on the metal surface, the contact resistance is higher than that of a carbon material, and when power is supplied to such a metal separator, the voltage drop increases, which may lead to a reduction in fuel cell performance. There is.
  • the first conventional technology is that the separator is oxidized during the reaction to generate power. Therefore, there is a problem that it is corroded during use.
  • the second conventional technique has a problem that the cost is increased due to the use of gold plating.
  • gold plating instead of gold plating, there is a method of applying a slurry mixed with a relatively inexpensive conductive oxide or graphite powder, but it may be partially damaged, and satisfactory results were not obtained.
  • the base material is made of metal, the strength can be maintained even if the thickness of the separation is reduced.
  • the conductive particles are formed by being fused and formed, the conductive particles are hardly peeled off and are formed as a porous layer. Alternatively, the contact area of the force sword is increased, and the contact resistance to the electrode is reduced.
  • the fuel cell separator since the amorphous metal is contained in at least a part of the material constituting the porous layer formed on the surface of the base material, the fuel cell separator has excellent corrosion resistance.
  • the separation method disclosed in Japanese Patent Application Laid-Open No. 2001-325966 has a problem that it takes a lot of time to manufacture since an amorphous metal must be laminated by a physical vapor deposition method.
  • the present inventors have conducted intensive studies to improve the above-mentioned drawbacks, and as a result, have found that by pressing a metal glass alloy, a separator excellent in superplasticity, strength, and conductivity can be obtained. Led to.
  • the Cu-based glass alloy in the above-mentioned application is prepared by melting an alloy having a specific composition of Zr and / or Hf and A1 and / or "or Ga and the balance of Cu, and rapidly solidifying it from a liquid state to a temperature of 45 K or more. It can be obtained by obtaining an amorphous phase rod (plate material) with a diameter (thickness) of 1 mm or more that shows the cooling liquid region ⁇ .
  • this Cu-based glass alloy was used as a material for separation, the corrosion resistance was insufficient.
  • the present invention relates to such a metallic glass alloy for separation, which is relatively inexpensive and excellent in corrosion resistance, workability, strength, and conductivity, and particularly excellent in the corrosion resistance required for the material for separation.
  • a metallic glass alloy for separation, which is relatively inexpensive and excellent in corrosion resistance, workability, strength, and conductivity, and particularly excellent in the corrosion resistance required for the material for separation.
  • a metal having a composition represented by atomic% represented by a composition formula Cu 100 — a — b Zr a A lb (where, 30 ⁇ a ⁇ 60, 0 ⁇ b ⁇ 15) is provided.
  • FIG. 1 is an illustration of a method for manufacturing a separator using the metallic glass alloy of the present invention.
  • FIG. 2 is a perspective view of a cell which is a minimum unit constituting the fuel cell.
  • Fig. 3 is a front view of the separator used for the fuel cell.
  • FIG. 4 is a chart showing power generation characteristics when the example 1 and the comparative example are used.
  • a composition by atomic% the composition formula C u 10 0 - a - b Z r a A 1 b (wherein, 3 0 ⁇ a ⁇ 6 0, 0 ⁇ b ⁇ 1 5).
  • Zr or a part of A1 may be replaced with Nb and / or Ta (each at most 10 atomic%).
  • Examples 1 and 2 are separators made of the metallic glass alloy of the composition of Claim 1
  • Example 3 is a separator made of the metallic glass alloy of the composition of Claim 2.
  • the maximum corrosion current density is the maximum value in the polarization curve in a 1 N sulfuric acid solution.
  • the hydrogen permeability was measured under the conditions of a differential pressure of 0.2 MPa and a temperature of 25.Because the hydrogen permeability of Examples 1 to 3 was below the detection limit of the measuring device, the hydrogen permeability was 7 X 1 0-below.
  • the currently used comparative example of the carponse parlay has a lower flexural strength, a larger volume resistance, a higher hydrogen permeability, and a greater thickness than the examples. However, it was inferior as fuel cell separation overnight.
  • the reason why the thickness of the comparative example is larger than that of the example is that the strength of the carpon separator itself is low, and it is easy to be damaged when it is removed from the mold after the pressure molding. This is because that.
  • the metallic glass separators of Examples 1 to 3 exhibited excellent performance in terms of volume resistance, hydrogen permeability, and thickness as a fuel cell separator, and metal was used in the fuel cell. The same level of performance as that of the carbon material was obtained with regard to corrosion, which is of the greatest concern during the process.
  • FIG. 4 shows the power generation characteristics when the embodiment 1 is incorporated into the fuel cell unit and when the comparative example is incorporated into the fuel cell unit. . From FIG. 4, it can be confirmed that Example 1 has power generation characteristics equal to or higher than the comparative example.
  • the method for producing a separator using the metallic glass alloy of the present invention comprises the following steps.
  • Step 1 The sheet 10 made of the metallic glass alloy of the present invention is placed in a mold 20 provided with groove-shaped irregularities in the chamber 30.
  • Step 2 The metal glass alloy sheet 10 and the mold 20 are heated to between the glass transition temperature and the crystallization temperature.
  • Step 3 A groove is formed in the metallic glass alloy sheet 10 by hot pressing.
  • the metallic glass alloy sheet 10 and the mold 20 are heated to a temperature between the glass transition temperature and the crystallization temperature. Requires heating.
  • the metallic glass alloy exhibits superplasticity in the temperature range between the transition temperature and the crystallization temperature, and can be easily press-formed by a mold heated to a high temperature, whereas the metallic glass alloy sheet 10 If the temperature is lower than the glass transition temperature, sufficient ductility cannot be obtained, and if the temperature is higher than the crystallization temperature, crystallization occurs, and it becomes general polycrystalline metal instead of metallic glass (metal in a liquid state by supercooling), This is because it is not possible to obtain the necessary corrosion resistance in the evening.
  • the heating and molding are preferably performed in an inert atmosphere. This is realized by filling the chamber 30 with an inert gas.
  • the thickness of the metallic glass alloy sheet 10 is desirably 50 to 250 m.
  • the metallic glass alloy of the present invention there is no grain boundary theoretically serving as a starting point of oxidation. Therefore, corrosion can be suppressed. It is also superior in strength and electrical conductivity to currently used carbon-based materials. Also, since the number of processes can be reduced as compared with the case where a carbon material is used, manufacturing costs can be reduced.
  • the metallic glass alloy of the present invention has an advantage that it can be manufactured at relatively low cost.
  • a metal that is relatively inexpensive and has excellent corrosion resistance, workability, strength, and conductivity, and in particular, has excellent corrosion resistance required for materials for separations This has the effect of obtaining a glass alloy.
  • a metal glass alloy which is relatively inexpensive and excellent in corrosion resistance, workability, strength, and conductivity, and particularly excellent in corrosion resistance required for a material for separation. .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

Un alliage amorphe pour un séparateur qui a une composition chimique en % atomique représentée par une formule empirique: Cu100-a-bZraAlb [avec 30 = a = 60 et 0 = b = 15]; et l'alliage amorphe dans lequel une partie de Zr ci-dessus ou Al ci-dessus sont remplacés par Nb et/ou Ta (10 % atomique ou moins de chaque élément). Cet alliage amorphe, qui peut se produire à un coût relativement bas, présente une excellente résistance à la corrosion, une très bonne aptitude au formage, une bonne résistance mécanique et une bonne électroconductivité, et en particulier une excellente résistance à la corrosion l'indiquant notamment pour un matériau de séparateur. Cet alliage amorphe ne présente théoriquement aucune limite de grain de cristal à partir de laquelle peut commencer une réaction d'oxydation, ce qui permet d'y interdire l'apparition de corrosion. L'alliage fait également preuve d'une résistance mécanique et d'une électroconductivité supérieures à celles des matériaux conventionnels à base de carbone. En outre, l'alliage permet la production d'un séparateur selon un procédé réduisant le nombre des opérations, par comparaison au cas d'un séparateur utilisant un matériau à base de carbone, ce qui aboutit à la suppression du coût de production d'un séparateur.
PCT/JP2004/018547 2003-12-12 2004-12-07 Alliage amorphe WO2005056858A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-414092 2003-12-12
JP2003414092A JP2005171333A (ja) 2003-12-12 2003-12-12 金属ガラス合金

Publications (1)

Publication Number Publication Date
WO2005056858A1 true WO2005056858A1 (fr) 2005-06-23

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JP (1) JP2005171333A (fr)
WO (1) WO2005056858A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210328233A1 (en) * 2020-04-21 2021-10-21 Hamilton Sundstrand Corporation Bulk metallic glass interconnect for high power density fuel cell

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2608296A1 (fr) * 2011-12-21 2013-06-26 The Swatch Group Research and Development Ltd. Collecteur de courant en métal amorphe
KR101501068B1 (ko) * 2013-06-07 2015-03-17 한국생산기술연구원 Zr기 비정질 합금조성물
US20150053312A1 (en) * 2013-08-23 2015-02-26 Jinn Chu Metallic Glass Film for Medical Application
CN104498845B (zh) * 2014-11-24 2017-01-25 中国科学院金属研究所 一种锆基非晶合金及其制备方法
CN114427068A (zh) * 2022-01-24 2022-05-03 盘星新型合金材料(常州)有限公司 铜基非晶合金及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0920968A (ja) * 1995-06-30 1997-01-21 Res Inst Electric Magnetic Alloys Ｃｕ基非磁性金属ガラス合金およびその製造法ならびに弾性作動体
JP2000178700A (ja) * 1998-12-15 2000-06-27 Japan Science & Technology Corp 高耐食性Ｚｒ系非晶質合金
JP2004091868A (ja) * 2002-08-30 2004-03-25 Japan Science & Technology Corp Ｃｕ基非晶質合金

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0920968A (ja) * 1995-06-30 1997-01-21 Res Inst Electric Magnetic Alloys Ｃｕ基非磁性金属ガラス合金およびその製造法ならびに弾性作動体
JP2000178700A (ja) * 1998-12-15 2000-06-27 Japan Science & Technology Corp 高耐食性Ｚｒ系非晶質合金
JP2004091868A (ja) * 2002-08-30 2004-03-25 Japan Science & Technology Corp Ｃｕ基非晶質合金

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210328233A1 (en) * 2020-04-21 2021-10-21 Hamilton Sundstrand Corporation Bulk metallic glass interconnect for high power density fuel cell

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