EP1753893A1 - Materiau enduit servant a former un materiau haute temperature et utilisation dudit materiau dans une pile a combustible - Google Patents

Materiau enduit servant a former un materiau haute temperature et utilisation dudit materiau dans une pile a combustible

Info

Publication number
EP1753893A1
EP1753893A1 EP05739581A EP05739581A EP1753893A1 EP 1753893 A1 EP1753893 A1 EP 1753893A1 EP 05739581 A EP05739581 A EP 05739581A EP 05739581 A EP05739581 A EP 05739581A EP 1753893 A1 EP1753893 A1 EP 1753893A1
Authority
EP
European Patent Office
Prior art keywords
coating
coated
solder
temperature
nickel
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.)
Withdrawn
Application number
EP05739581A
Other languages
German (de)
English (en)
Inventor
Hans-Heinrich Angermann
Herbert Damsohn
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.)
Mahle Behr GmbH and Co KG
Original Assignee
Behr GmbH and Co KG
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 Behr GmbH and Co KG filed Critical Behr GmbH and Co KG
Publication of EP1753893A1 publication Critical patent/EP1753893A1/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • H01M8/0215—Glass; Ceramic materials
    • H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
    • 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
    • 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
    • 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 invention relates to a coated material according to the preamble of claim 1.
  • SOFC fuel cells are usually operated at operating temperatures of 800 ° C.
  • stainless steel is considered for the interconnector plates of the fuel cell and for the heat exchangers surrounding it.
  • CR compounds on the cathode side in normal air evaporate from the materials, which lead to high electrical losses in the SOFC fuel cell.
  • DE 100 25 108 A1 discloses a high-temperature material made of a chromium oxide-forming iron alloy with up to 2% by weight of at least one oxygen-affine element from the group (Y, Ce, Zr, Hf and La) and up to 2% by weight of one Elements M from the group (Mn, Ni and Co), which forms a spinel phase of the type MCr 2 O with chromium oxide at high temperatures, up to 2% by weight of a further element from the group (Ti, Hf, Sr, Ca and Ze), which is the electrical conductivity of oxides based on Cr
  • the chromium content of the iron alloy is in particular 12 to 28% by weight, in particular 17 to 25% by weight.
  • This high-temperature material is therefore a ferritic chrome steel. With such a material, a spinel phase of the type MCr MCO ⁇ forms at the chromium dioxide / gas interface with the Cr 2 ⁇ 3. This has lower Cr evaporation rates.
  • This high-temperature material can be used in particular for interconnector plates of a high-temperature fuel cell (SOFC), spark plugs or electrodes.
  • SOFC high-temperature fuel cell
  • ferritic alloys are not suitable for components in the periphery of SOFC, in particular for heat exchangers, because of their insufficient strength and because of the lack of thermal resistance of their oxide layers at high temperatures, in particular from 900 ° C.
  • recyclate Heat exchanger in which recycled gas (hydrogen-depleted reformate gas), which contains about 20% water in a stationary operation, is cooled.
  • Suitable metallic materials are usually very high alloyed or nickel-based materials and therefore expensive.
  • a steel or stainless steel material which has a nickel-based coating with a chromium content of at least 7% by weight.
  • a nickel-chromium spinel is formed in the coating from NiO and Cr 2 ⁇ 3, which significantly reduces the formation rates of volatile Cr compounds.
  • a relatively inexpensive base material can be used, which is coated, so that the material and manufacturing costs are relatively low. Effective protection against a significant loss of chromium enables high-temperature fuel cells with a long service life, for example. Under certain circumstances, a nickel-chromium spinel layer also protects against oxidation.
  • the chromium content in the coating is below 50% by weight, preferably below 35% by weight.
  • the coating can preferably be formed by a solder, with commercially available nickel-chromium-based solders in particular also being suitable.
  • the coating preferably contains elements which lower the melting point, such as, in particular, silicon, boron and / or phosphorus. These lower the temperatures required for the formation of the coating and thus also reduce the manufacturing costs. Other elements such as in particular copper, iron and / or tungsten as well as unavoidable impurities are also possible.
  • the coating is preferably applied by means of roll cladding, thermal spraying, CVD or PVD processes, via sol-gel processes, by means of cold gas spraying, galvanic or chemical coating, dipping, spraying on or pumping through nickel solder paste.
  • roll cladding thermal spraying, CVD or PVD processes
  • sol-gel processes by means of cold gas spraying, galvanic or chemical coating, dipping, spraying on or pumping through nickel solder paste.
  • other methods are also possible.
  • Such a coated material is used in particular for interconnector plates, other components of high-temperature fuel cells, such as, for example, heat exchangers, burners, etc., electrodes or spark plugs, but other applications, in particular at high temperatures, are also possible.
  • a coating 2 which essentially consists of nickel with a chromium content of at least 7% by weight.
  • Cr-containing stainless steels form Cr 2 ⁇ 3 -based oxide layers when exposed to air.
  • Chromium contains, forms at high temperatures on the surface
  • NiCr 2 O 4 nickel-chromium spinel
  • This NiCr spinel has greatly reduced formation rates of volatile Cr compounds.
  • the proportion of NiCr spinel in the surface oxides increases up to a Cr proportion of approx. 30% by weight. If the Cr content were increased more and more, for example to a content greater than 50% by weight, oxides based on Cr 2 O 3 are formed again and again, which would increase the evaporation of Cr compounds again. What is important about the mechanism of formation of NiCr 2 O 4 is that the nickel-chromium spinel forms on the Cr 2 ⁇ 3 layer.
  • the material coated according to the invention thus differs from the customary high-temperature materials, which are often alloyed with silicon and in which a stable SiOr layer is to form as a diffusion barrier, which, however, takes place under the Cr 2 ⁇ 3 layer. With these conventional materials, this Cr 2 O 3 will definitely evaporate in the initial states of the high-temperature design. Under certain circumstances, the NiCr 2 O layer provides protection against oxidation in a water-containing atmosphere.
  • a semi-finished product made of stainless steel material for interconnect plates or for components on the SOFC periphery is provided with a NiCr layer by means of roll plating.
  • NiCr heat conductor alloys which can additionally be alloyed with silicon, calcium, cerium and / or other elements, are suitable as alloys.
  • ferritic materials can also be plated, in particular for interconnect plates. In this case, a thin layer of austenitic NiCr on both sides does not change the desired low thermal expansion coefficient of the composite material “ferritic core” and “austenitic layer” or changes it only insignificantly.
  • the semi-finished material is to serve as sheets for forming a heat exchanger for the SOFC, it is sufficient if the sheet is roll-coated on one side, since the base material will generally be austenitic and the formation of volatile Cr compounds only occurs in the cathode air for the channel leading SOFC can have a negative impact.
  • the coating with a view to increasing the oxidation resistance, since the water-containing atmosphere is only present in one passage of the heat exchanger. The same applies to other coating processes.
  • the NiCr coating material for interconnector plates or peripheral components can be applied by means of thermal spraying, CVD or PVD processes, sol-gel processes, by means of cold gas spraying, galvanically or chemically, or the like.
  • the material can be applied locally, for example by means of thermal spraying using a mask.
  • nickel-based solders can also be applied locally by means of thermal spraying and cold gas spraying. These known solders often consist essentially of nickel with a minimum content of 7% by weight of chromium.
  • elements that lower the melting point such as silicon and / or boron and / or phosphorus. Further elements such as copper, iron, tungsten can also be included.
  • a NiCrP solder alloy e.g. galvanically or chemically
  • a NiCrP coating can be used directly, i.e. as a ternary alloy, to be electrodeposited.
  • Another possibility is chemically or galvanically a Ni-P layer, e.g. Ni10P, to be deposited and a Cr layer placed thereon, for example chemically or by means of PVD. The thickness of the chrome layer then determines the chrome content of the alloy.
  • the semi-finished material When using the semi-finished material as an interconnector plate, it is preferably heated to the soldering temperature of the material before installation in the SOFC.
  • the solder alloy melts, the melting point-lowering phosphor diffuses into the base material due to a suitably long holding time at the soldering temperature, so that the coating of the interconnector plate cannot melt again during operation in the SOFC.
  • the NiCrP coating as a solder alloy is also particularly suitable for the production of components.
  • the coating then has a triple function as a solder, as a surface to reduce the evaporation rate of Cr compounds and as a protective layer against oxidation. In this case, the coated semi-finished material is of course not heated to the soldering temperature before being assembled into a component.
  • a chemical composition of the NiCrP alloy is, for example, that of the commercial alloys Ni107, Ni14Cr10P, N 12 or Ni25CM0P.
  • the analog use of nickel-based solder foils for the coating of interconnect plates is also possible.
  • the use of such solder foils for the joining of components with the double function as solder and coating only partially solves the problem of the formation of volatile Cr compounds, since the solder foil tends to only hit one side of the channel during soldering, that is Channel is not completely wetted by the nickel-based solder foil. This means that approx. 50% of the heat exchanger surface remains unoccupied by the Ni-based solder foil.
  • solder paste and solder tape are a mixture of powdered nickel-based solder powder and organic substances such as binders and solvents, which together with the powder result in a mass with a certain viscosity.
  • the solder paste can be applied by dipping, spraying, dosing, etc.
  • the solder tape is glued on.
  • the solder tape can be shaped with a desired contour, e.g. by means of punching.
  • a nickel-based solder paste flows through them.
  • the component for heating cathode air for the SOFC only the channel carrying the cathode air is preferably flowed through and thus coated. This is followed by heating in a suitable vacuum or inert gas oven to the soldering temperature of the solder used, so that the solder paste is melted and forms a tight layer. This usually forms a closed protective layer after the heat treatment.
  • solders containing nickel and chromium are suitable as solders, P-containing solders such as Ni14Cr or Ni25Cr10P being particularly suitable.
  • solders containing nickel, chromium and phosphorus are particularly advantageous to heat-treat the solders containing nickel, chromium and phosphorus at temperatures above the recommended soldering temperature. Temperatures are preferably 50 K higher, particularly preferably 100 K higher than the recommended soldering temperature.
  • the solders are then on the one hand very flowable and spread easily on a surface of a workpiece to be coated, so that even surface areas that were not covered with solder paste due to a coating defect are nevertheless covered with a NiCr layer after the heat treatment.
  • the solidus and liquidus temperatures of the NiCrP solders are so low that a heat treatment temperature that is higher than the recommended soldering temperature does not result in severe damage to the base material, for example due to coarse grain formation. With stainless steel as the base material, however, a heat treatment temperature of 1200 ° C should not be exceeded.
  • a NiCrP solder can also contain other elements, such as boron.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Fuel Cell (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne un matériau enduit servant à former un matériau haute température. Ce matériau se compose d'une matière de base (1), constituée par un acier ou un acier spécial, et d'un revêtement (2) à base de nickel présentant une proportion de chrome d'au moins 7 % en poids. Ladite invention concerne également la fabrication dudit matériau.
EP05739581A 2004-04-02 2005-04-04 Materiau enduit servant a former un materiau haute temperature et utilisation dudit materiau dans une pile a combustible Withdrawn EP1753893A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004017001 2004-04-02
PCT/EP2005/003503 WO2005095672A1 (fr) 2004-04-02 2005-04-04 Materiau enduit servant a former un materiau haute temperature et utilisation dudit materiau dans une pile a combustible

Publications (1)

Publication Number Publication Date
EP1753893A1 true EP1753893A1 (fr) 2007-02-21

Family

ID=34966985

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05739581A Withdrawn EP1753893A1 (fr) 2004-04-02 2005-04-04 Materiau enduit servant a former un materiau haute temperature et utilisation dudit materiau dans une pile a combustible

Country Status (2)

Country Link
EP (1) EP1753893A1 (fr)
WO (1) WO2005095672A1 (fr)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998603A (en) * 1973-08-29 1976-12-21 General Electric Company Protective coatings for superalloys
US5643690A (en) * 1994-11-11 1997-07-01 Kabushiki Kaisha Toshiba Molten carbonate fuel cell
AUPN173595A0 (en) * 1995-03-15 1995-04-06 Ceramic Fuel Cells Limited Fuel cell interconnect device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005095672A1 *

Also Published As

Publication number Publication date
WO2005095672A1 (fr) 2005-10-13

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