[go: up one dir, main page]

WO2011053041A2 - Acier inoxydable ferritique pour piles à combustible à oxyde solide et matériau de connexion utilisant cet acier - Google Patents

Acier inoxydable ferritique pour piles à combustible à oxyde solide et matériau de connexion utilisant cet acier Download PDF

Info

Publication number
WO2011053041A2
WO2011053041A2 PCT/KR2010/007520 KR2010007520W WO2011053041A2 WO 2011053041 A2 WO2011053041 A2 WO 2011053041A2 KR 2010007520 W KR2010007520 W KR 2010007520W WO 2011053041 A2 WO2011053041 A2 WO 2011053041A2
Authority
WO
WIPO (PCT)
Prior art keywords
stainless steel
weight
less
ferritic stainless
added
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.)
Ceased
Application number
PCT/KR2010/007520
Other languages
English (en)
Korean (ko)
Other versions
WO2011053041A3 (fr
Inventor
김규영
김도형
전재호
서형석
윤대원
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
POSTECH Academy Industry Foundation
Original Assignee
POSTECH Academy Industry Foundation
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 POSTECH Academy Industry Foundation filed Critical POSTECH Academy Industry Foundation
Publication of WO2011053041A2 publication Critical patent/WO2011053041A2/fr
Publication of WO2011053041A3 publication Critical patent/WO2011053041A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

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
    • H01M8/021—Alloys based on iron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • 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
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide 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 relates to stainless steel for fuel cells operating at high temperatures. More specifically, a solid oxide fuel cell that operates at high temperatures because it can obtain excellent oxidation resistance and electrical conductivity without containing rare earth elements such as La and Y, which are expensive and difficult in steelmaking, and have low high temperature Cr volatility. It can be used as a material for (SOFC: Solid Oxide Fuel Cell), and in particular, it relates to a ferritic stainless steel (ferritic stainless steel) suitable for the connection material of Planar Solid Oxide Fuel Cells (PSOFC).
  • SOFC Solid Oxide Fuel Cell
  • a fuel cell is a power generation device that generates electrical energy from hydrogen energy.
  • fuel cells are phosphate type (PAFC; Phosphoric Acid Fuel Cell), molten carbonate type (MCFC; Molten Carbonate Fuel Cell), solid oxide type (SOFC), and polymer electrolyte membrane fuel cells.
  • PEMFC Polymer Electrolyte Membrane Fuel Cell (PEMFC), and its operating temperature varies depending on the type of fuel cell.
  • the solid oxide type is about 1,000 °C
  • the molten carbonate type is about 650 °C
  • the phosphate type is about 200 °C
  • the polymer electrolyte type It is about 100 degrees C or less.
  • the dual SOFC has the advantage of high power generation efficiency by operating at the highest temperature, and is divided into tubular SOFC and flat SOFC.
  • the manufacturing process is simpler than the tubular SOFC, which is advantageous for commercialization and large capacity.
  • the main components of the plate-type SOFC is composed of a unit cell consisting of a solid oxide electrolyte and an electrode and a connecting material for forming a stack by connecting the unit cells.
  • the SOFC connection material is a material that electrically connects and separates each unit cell and serves as a passage between fuel and air supplied to each unit cell, and has excellent stability at high temperature, high electrical conductivity, and a unit of thermal expansion coefficient. Properties that must be similar to the coefficient of thermal expansion of a cell are required.
  • the connecting material may also be termed 'bipolar plate' or 'separator', depending on the function of the fuel cell.
  • the SOFC connector As a material of the SOFC connector, conventionally, a solid oxide having excellent stability at high temperature was used, but the solid oxide connector has a weak mechanical strength, a high production cost, and difficult processing.
  • ferritic stainless steel is cheaper than other metal materials, and its coefficient of thermal expansion is similar to that of unit cells.However, due to the formation of an oxide layer at high temperatures, the increase of electrical resistance and the volatilization of chromium (Cr) on the surface. There is a disadvantage of contaminating the electrode.
  • the ferritic stainless steel developed for the SOFC connector has been added to the rare earth element such as lanthanum (La) and yttrium (Y) to reduce the growth rate of the oxide layer and improve the electrical conductivity.
  • rare earth elements such as lanthanum (La) and yttrium (Y) have been a cause for lowering the productivity and increasing the price of SOFC coupling materials because the materials themselves are expensive and rare and make steelmaking difficult.
  • the present invention is to solve the above-mentioned problems of the prior art, and is excellent in oxidation resistance and electrical conductivity and at high temperature without adding rare earth elements such as lanthanum (La) or yttrium (Y), which make steelmaking difficult and expensive.
  • An object of the present invention is to provide a ferritic stainless steel for fuel cell connection material having a low volatilization rate of chromium (Cr).
  • Another object of the present invention is to provide a fuel cell connection material having a low cost and excellent performance compared to the existing connection material.
  • the present invention Cr: more than 20% by weight to 35% by weight, Mn: 1% by weight or less, Nb: 0.3% to 5% by weight, for the fuel cell consisting of the remaining Fe and unavoidable impurities Provide ferritic stainless steel.
  • the content of Nb is characterized in that it is contained in more than 0.8% to 1.5% by weight.
  • ferritic stainless steel for fuel cells may be further selected from C: 0.03% by weight, N: 0.03% by weight, Mo: 5.0% by weight, Cu: 3.0% by weight, or less selected from Ti, V, or Zr.
  • the above can be contained in 0.5 weight% or less.
  • the present invention also provides a connecting material made of a ferritic stainless steel of the above composition.
  • the 'connector' refers to a device for connecting one part to another part (electrically, mechanically, or electrically and mechanically).
  • the connector can perform several functions in the fuel cell, for example, isolation and containment of reactant gas, and electrical connection of the cells in series by providing a low resistance path to current.
  • the connecting material may also be referred to as a bipolar plate or a separator, depending on the function of the fuel cell.
  • Cr is an element necessary for securing basic corrosion resistance as ferritic stainless steel, and when Cr content is 20% by weight or less, the corrosion resistance required as a fuel cell connecting material is not sufficient. In addition, when Cr content exceeds 35 weight%, the sigma phase which is a secondary phase precipitates, and the characteristic of a material falls. Therefore, it is necessary to maintain Cr content in the range of 20 weight%-35 weight%.
  • Mn is a component having the effect of reducing S that is mixed with inevitable impurities and solid solutioned to ferritic stainless steel, and suppresses grain boundary segregation of S and is produced by S during hot rolling of stainless steel. It is an effective element to prevent cracking and can be added as necessary. On the other hand, such an effect can be exerted when added in an amount of 0.001% by weight or more, and when Mn exceeds 1.0% by weight, since the oxidation rate is greatly increased, Mn is most preferably added in the range of 0.001 to 1.0% by weight. desirable.
  • Nb reacts with C and N in stainless steel to form carbonitrides to fix C and N, it is known to prevent deterioration of corrosion resistance due to Cr carbonitride precipitation and to improve the press formability of ferritic stainless steel. It is an ingredient.
  • the content of Nb is less than 0.3% by weight, it is difficult to sufficiently obtain the above effects, and when the content of Nb is more than 5% by weight, the effect is saturated, so it is preferably contained in the range of 0.3% by weight to 5% by weight.
  • Nb is added in the range of more than 0.8% by weight to 1.5% by weight, which is not the case when Nb is added in excess of 0.8% by weight.
  • the electrical conductivity may be further improved, and when Nb is added in an amount of 1.5 wt% or less, the high temperature Cr volatilization rate may be lower than that in the case where it is added in excess of 1.5 wt%. This may be due to the phenomenon that the concentration of Nb that precipitates or segregates at the interface between the oxide layer and the alloy is rather reduced compared to the case where Nb is added in excess of 1.5% by weight.
  • C and N react with Cr in the ferritic stainless steel for fuel cells to precipitate as Cr carbonitride at grain boundaries, thereby degrading the corrosion resistance of the stainless steel. Therefore, it is preferable to keep content of C and N low at 0.03 weight% or less, and it is more preferable to keep it at 0.015 weight% or less, respectively.
  • Mo is an effective element for suppressing the corrosion of ferritic stainless steel and can be added as necessary. However, when added in excess of 5.0% by weight, the brittleness of the stainless steel is sharply increased, making steelmaking difficult, so it is added in less than 5.0% by weight, more preferably in the range of 0.1 to 3.0% by weight.
  • Cu may be optionally added to improve the corrosion resistance of the ferritic stainless steel, and when added in excess of 3.0% by weight, the hot workability is lowered, so the amount may be added in an amount of 3.0% by weight or less, and more preferably in an amount of 2.0% by weight or less. do.
  • Ti, V, and Zr react with C and N in stainless steel to form carbonitrides, thereby improving the formability of stainless steel. Therefore, if necessary, Ti, V, and Zr may be added so that the sum of the three components is 0.5% by weight or less. More preferably at most 0.3 wt.
  • the rare earth element or the element having higher oxygen affinity than Cr is added at 0.1 wt% or less, it may be added when additional oxidation resistance is required by increasing the oxidation resistance of the material.
  • Si used for deoxidation in the solvent step of stainless steel may contain 0.1 wt% or less.
  • Other S may also be contained in an amount of 0.1 wt% or less, more preferably 0.01 wt% or less.
  • Stainless steel for fuel cells and a fuel cell connecting material using the same according to the present invention can be expected the following effects.
  • the ferrite stainless steel since the ferrite stainless steel is used, it is possible to enjoy the unique effects of the ferritic stainless steel, that is, the manufacturing is easy, the manufacturing cost is low, and the difference in coefficient of thermal expansion with the ceramic constituting the unit cell is not great.
  • the ferritic stainless steel according to the present invention is expensive and does not use rare earth elements such as lanthanum (La) or yttrium (Y), which makes steelmaking difficult, so that mass production is easier and can be manufactured at a lower cost than before. do.
  • rare earth elements such as lanthanum (La) or yttrium (Y)
  • the ferritic stainless steel according to the present invention can not only obtain excellent oxidation resistance and electrical conductivity comparable to that of expensive lanthanum (La) or yttrium (Y), but can also lower the volatilization of Cr at high temperatures. .
  • FIG. 2 is an evaluation of electrical resistance in order to compare the electrical conductivity of stainless steels manufactured according to Examples and Comparative Examples of the present invention, and the surface contact resistance (ASR) after oxidizing for 100 hours in 800 ° C. air. It shows the result of measuring.
  • Figure 3 shows the results of measuring the amount of Cr volatilized for 24 hours in 800 °C air as evaluating the Cr volatilization rate of the stainless steel prepared according to the Examples and Comparative Examples of the present invention.
  • the present inventors prepared a stainless steel having a composition as shown in Table 1, by comparing each characteristic, and evaluated whether the stainless steel according to the embodiment of the present invention is suitable for the fuel cell connecting material, the specific manufacturing method Same as
  • Example 1 of the present invention by using a vacuum induction melting method, an alloy of the composition shown in Table 1 was made, the prepared alloy was subjected to homogenization treatment at 1200 °C for at least 24 hours and then quenched and cut to a thickness of 2 mm A stainless steel sheet was prepared.
  • the oxidation resistance evaluation of the stainless steel specimens prepared as described above was performed by measuring the change in weight while oxidizing in an air atmosphere of 800 ° C. similar to the operating environment of the SOFC fuel cell, and the result was as shown in FIG. 1.
  • Example of this invention shows the oxidation resistance equivalent to the comparative example 3 which adds the rare earth element La to stainless steel, and the comparative example 4 which added Y.
  • the specimens of the above composition were oxidized in air at 800 ° C. for 100 hours, similar to the operating environment of the fuel cell, and then sampled using a two-probe galvanodynamic polarization method.
  • the contact resistance of the alloy was measured under a condition of 1 cm 2 and the scan speed of 10 mV, and the result was as shown in FIG. 2.
  • FIG. 2 is a comparison of the area contact resistance (ASR) measured in order to compare the electrical conductivity of the examples of the present invention and the comparative example.
  • ASR area contact resistance
  • Example 2 in which Ti was added instead of Nb, the electrical conductivity was significantly reduced.
  • Example 2 in which 4% by weight of Nb was added, and Example 3, in which 0.3% by weight of Nb was added, showed similar electrical conductivity to Comparative Example 1.
  • Example 1 in which 1% by weight of Nb was added, showed a Cr volatilization rate similar to that of Comparative Example 2 in which Ti was added instead of Nb.

Landscapes

  • 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

La présente invention concerne un acier inoxydable, ne comprenant pas d'éléments des terres rares coûteux qui ne simplifient pas la fabrication de l'acier. L'acier inoxydable selon l'invention possède une haute résistance à l'oxydation et une grande conductivité électrique, tout en présentant une faible vitesse de volatilisation du chrome (Cr) à haute température, ce qui fait qu'il est adapté pour être utilisé dans un matériau de connexion pour piles à combustible. L'acier inoxydable selon l'invention comprend : 20 à 35 % en poids de Cr; 1 % en poids ou moins de Mn; 0,3 à 5 % en poids de Nb, le reste étant constitué de fer et d'impuretés inévitables.
PCT/KR2010/007520 2009-10-30 2010-10-29 Acier inoxydable ferritique pour piles à combustible à oxyde solide et matériau de connexion utilisant cet acier Ceased WO2011053041A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20090104018 2009-10-30
KR10-2009-0104018 2009-10-30

Publications (2)

Publication Number Publication Date
WO2011053041A2 true WO2011053041A2 (fr) 2011-05-05
WO2011053041A3 WO2011053041A3 (fr) 2011-09-22

Family

ID=43922866

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2010/007520 Ceased WO2011053041A2 (fr) 2009-10-30 2010-10-29 Acier inoxydable ferritique pour piles à combustible à oxyde solide et matériau de connexion utilisant cet acier

Country Status (1)

Country Link
WO (1) WO2011053041A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11228041B2 (en) 2017-03-31 2022-01-18 Osaka Gas Co., Ltd. Electrochemical device, energy system and solid oxide fuel cell
US11233262B2 (en) 2017-03-31 2022-01-25 Osaka Gas Co., Ltd. Electrochemical element, electrochemical module, electrochemical device, energy system, solid oxide fuel cell and manufacturing method for electrochemical element
CN114867879A (zh) * 2020-04-15 2022-08-05 日铁不锈钢株式会社 铁素体类不锈钢材及其制造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1553198A4 (fr) * 2002-06-14 2005-07-13 Jfe Steel Corp Acier inox ferritique thermoresistant et son procede de production
WO2005064030A1 (fr) * 2003-12-26 2005-07-14 Jfe Steel Corporation Acier contenant du cr ferritique
EP1726674B1 (fr) * 2004-03-18 2017-05-10 JFE Steel Corporation Matériau métallique pour élément conducteur, séparateur pour pile à combustible utilisant celui-ci et pile à combustible incluant ce dernier
KR100931457B1 (ko) * 2007-12-20 2009-12-11 주식회사 포스코 고분자 연료전지 분리판용 스테인리스강의 표면 개질방법

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11228041B2 (en) 2017-03-31 2022-01-18 Osaka Gas Co., Ltd. Electrochemical device, energy system and solid oxide fuel cell
US11233262B2 (en) 2017-03-31 2022-01-25 Osaka Gas Co., Ltd. Electrochemical element, electrochemical module, electrochemical device, energy system, solid oxide fuel cell and manufacturing method for electrochemical element
TWI763812B (zh) * 2017-03-31 2022-05-11 日商大阪瓦斯股份有限公司 電化學裝置、能源系統、及固態氧化物型燃料電池
CN114867879A (zh) * 2020-04-15 2022-08-05 日铁不锈钢株式会社 铁素体类不锈钢材及其制造方法

Also Published As

Publication number Publication date
WO2011053041A3 (fr) 2011-09-22

Similar Documents

Publication Publication Date Title
KR101411671B1 (ko) 페라이트 크롬강
WO2012091446A2 (fr) Cellule unitaire de pile à combustible à oxyde solide supportée par un métal, son procédé de préparation et empilement de piles à combustible à oxyde solide utilisant la cellule unitaire
WO2011053041A2 (fr) Acier inoxydable ferritique pour piles à combustible à oxyde solide et matériau de connexion utilisant cet acier
WO2021241812A1 (fr) Acier inoxydable pour séparateur de pile à combustible
KR20110047999A (ko) 고체 산화물 연료전지용 페라이트계 스테인리스강 및 이를 이용한 연결재
CN1948539A (zh) 燃料电池互连件用的合金
WO2019045302A1 (fr) Pile à combustible à oxyde solide supportée par du métal et son procédé de fabrication
SE527933C2 (sv) Värmebeständigt stål
WO2022255731A1 (fr) Tôle d'acier présentant une excellente hydrophilie et une excellente conductivité
JP5259480B2 (ja) 固体酸化物形燃料電池用インターコネクタ及びその形成方法
WO2023038167A1 (fr) Pile à combustible à oxyde solide à support métallique comprenant une couche de contact
WO2022255732A1 (fr) Plaque d'acier présentant un excellent caractère hydrophile et une excellente conductivité
WO2022114652A1 (fr) Acier inoxydable austénitique pour séparateur de pile à combustible présentant une résistance de contact améliorée et son procédé de fabrication
WO2018117469A1 (fr) Acier inoxydable destiné à une plaque de séparation de pile à combustible polymère et présentant une excellente résistance de contact, et procédé de fabrication associé
WO2021125436A1 (fr) Acier inoxydable pour séparateur de pile à combustible à polymère présentant une excellente résistance à la corrosion
WO2024158099A1 (fr) Électrode à air de pérovskite ayant des nanostructures, et son procédé de fabrication
WO2019245076A1 (fr) Procédé destiné à fabriquer de l'acier inoxydable pour séparateur de pile à combustible polymère ayant une excellente résistance de contact
WO2024150916A1 (fr) Électrolyte de zircone pour cellule d'électrolyse à oxyde solide, et son procédé de préparation
KR101013845B1 (ko) 중저온 평판형 고체산화물 연료전지용 밀봉유리 제조방법
WO2025102454A1 (fr) Acier inoxydable ferritique à haute teneur en chrome pour interconnexion de pile à combustible à oxyde solide
KR102073158B1 (ko) 나노 산화물이 분산된 페라이트 강을 포함하는 고체산화물 연료 전지용 분리판 및 이의 제조 방법
CN101333613B (zh) 一种中温平板式固体氧化物燃料电池金属连接体用镍基膨胀合金
WO2019088728A2 (fr) Vitrocéramique li2s-p2s5-b2s3 et batterie secondaire entièrement solide en contenant à titre d'électrolyte solide
WO2025127614A1 (fr) Tôle d'acier austénitique non revêtue pour plaque bipolaire pour électrolyse d'eau alcaline
WO2025127831A1 (fr) Plaque en titane pour plaque bipolaire présentant une excellente conductivité électrique de surface et une excellente durabilité et son procédé de fabrication

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10827125

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10827125

Country of ref document: EP

Kind code of ref document: A2