WO2012155333A1 - Heat-resistant metal connecting component, method producing the same and solid oxide fuel cell stack - Google Patents

Heat-resistant metal connecting component, method producing the same and solid oxide fuel cell stack Download PDF

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Publication number
WO2012155333A1
WO2012155333A1 PCT/CN2011/074141 CN2011074141W WO2012155333A1 WO 2012155333 A1 WO2012155333 A1 WO 2012155333A1 CN 2011074141 W CN2011074141 W CN 2011074141W WO 2012155333 A1 WO2012155333 A1 WO 2012155333A1
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Prior art keywords
alloy powder
fuel cell
metal connector
coating
solid oxide
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PCT/CN2011/074141
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French (fr)
Chinese (zh)
Inventor
王蔚国
刘武
官万兵
金乐
李方虎
马晓
苏志国
Original Assignee
中国科学院宁波材料技术与工程研究所
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Priority to PCT/CN2011/074141 priority Critical patent/WO2012155333A1/en
Publication of WO2012155333A1 publication Critical patent/WO2012155333A1/en

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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
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • 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

Definitions

  • the invention belongs to the technical field of solid oxide fuel cells, and in particular relates to a high temperature resistant metal connector and a solid oxide fuel cell stack. Background technique
  • solid oxide fuel cells SOFC
  • metallic materials are the preferred choice for connectors in solid oxide fuel cell stacks, especially ferritic alloy materials such as Fe-16Cr, Fe. ⁇ 22Cr and so on.
  • Fe-Cr alloy joints undergo high temperature oxidation at the operating temperature of the SOFC, and the Cr element on the surface is also easily volatilized, thereby accelerating the decay of the life of the stack.
  • the prior art generally avoids high temperature oxidation and volatilization of Cr by preparing a dense high temperature protective coating on the surface of the connector.
  • high temperature protective coatings there are mainly three types of high temperature protective coatings:
  • Nitride coatings are mainly prepared by vacuum deposition (PVD) methods, including CrN/AlN,
  • the nitride coating can obtain a lower surface resistance of the metal joint, effectively preventing high temperature oxidation and Cr element volatilization.
  • the high temperature instability of the nitride, and the high preparation cost and low deposition rate of the coating limit its application.
  • the spinel coating has better high temperature properties, mainly including Cr-containing spinel and Cr-free spinel.
  • Cr-containing spinel still has the problem of Cr element volatilization
  • Cr-free spinel such as (Mn, Co) 3 4 4
  • the spinel is generally formed by a wet coating and then sintering at a high temperature for hundreds of hours to form a coating or a coating of a coating such as Mn or Co on a connecting member, and the preparation method is complicated and unfavorable for a wide range of industries. Promotion.
  • the perovskite coating structure is usually AB0 3 type, wherein A is La, Ce, Pr or Nb, etc., B is Co, Mn, Fe, Cr, Cu or V, etc., such as LaCr0 3 , LaMn0 3 or La (Co , Fe) 0 3 and so on.
  • the perovskite coating can be prepared by various methods such as plasma spraying, wet spraying, sintering or atomization deposition, and can effectively prevent high temperature oxidation and Cr element volatilization. The most common coating for the fitting.
  • the plasma spray method is widely used because of its advantages of a process cartridge and a low cost.
  • the metal connecting member is subjected to surface treatment such as sand blasting. Since the high pressure gas of 0.5 MPa to 0.6 MPa is required in the blasting process, the metal connecting member is easily deformed. Affect the use of metal connectors.
  • the perovskite coating has a low bonding force to the surface of the metal connector, has a high ohmic resistance value, and is easily detached at a high temperature, which affects the output performance and service life of the solid oxide fuel cell stack. Summary of the invention
  • the technical problem to be solved by the present invention is to provide a high temperature resistant metal connecting member, a manufacturing method thereof and a solid oxide fuel cell stack.
  • the high temperature resistant metal connecting member provided by the present invention can be used at 850 ° C.
  • the ohmic resistance value is lower in the solid oxide fuel cell stack.
  • the invention provides a high temperature resistant metal connector, comprising:
  • a perovskite coating compounded on the surface of the alloy powder coating is A perovskite coating compounded on the surface of the alloy powder coating.
  • the alloy powder in the alloy powder coating layer is a Cr-based alloy powder.
  • the Cr-based alloy powder is a Fe-Cr alloy powder or a Ni-Cr alloy powder.
  • the alloy powder in the alloy powder coating has a particle size of 0.01 mm to 0.15 mm.
  • the alloy powder coating has a thickness of 0.02 mm to 0.2 mm.
  • the perovskite in the 4 ornithose coating is cerium-doped lanthanum manganate, cerium-doped lanthanum cobaltate or cerium and iron-doped lanthanum cobaltate.
  • the perovskite has a particle size of 0.01 mm to 0.15 mm in the perovskite coating.
  • the perovskite coating has a thickness of from 0.02 mm to 0.15 mm.
  • the invention also provides a preparation method of the high temperature resistant metal connector according to the above technical solution, comprising the following steps:
  • the present invention also provides a solid oxide fuel cell stack, comprising: a stacked structure and a housing accommodating the stacked structure, wherein the stacked structure comprises:
  • More than two solid oxide fuel cells comprising a current collector layer, a cathode, an electrolyte layer and an anode stacked in sequence;
  • the high temperature resistant metal connector comprises: a metal connector substrate; an alloy powder coating composited on the surface of the metal connector substrate; and composited on the surface of the alloy powder coating Perovskite coating.
  • the invention provides an alloy powder coating between the metal connector substrate and the perovskite coating, and the alloy powder coating can form a rough surface on the metal connector substrate, thereby eliminating the need for sandblasting.
  • the metal connector substrate is not deformed.
  • the alloy powder coating can enhance the compatibility between the metal connector substrate and the perovskite coating, thereby improving the bonding force between the perovskite coating and the metal connector substrate, and the perovskite coating is not easy. Shedding, more suitable for use in high temperature environments, such as in solid oxide fuel cell stacks operating at 850 ° C, is not prone to high temperature oxidation.
  • the high temperature resistant metal connector provided by the invention can be used for a solid oxide fuel cell stack, and has a tight interface and a low ohmic resistance value, can improve the output performance of the fuel cell stack, reduce the attenuation speed, and ultimately improve the service life.
  • the output performance, output power density, ohmic resistance value, etc. of the solid oxide fuel cell stack prepared by the high temperature resistant metal connecting member provided by the present invention are substantially indistinguishable from the corresponding properties of the uncoated metal connecting member.
  • FIG. 1 is a schematic structural view of a high temperature resistant metal connector according to an embodiment of the present invention.
  • FIG. 2 is a schematic structural view of a solid oxide fuel cell stack prepared according to Embodiment 2 of the present invention
  • FIG. 3 is a current-electrical circuit of a single cell 13 and a fuel cell stack unit 18 according to Embodiment 2 of the present invention
  • Pressure-power density curve ;
  • FIG. 5 is an impedance curve of the unit cell 13 and the fuel cell stack unit 18 according to Embodiment 2 of the present invention
  • FIG. 6 is an impedance curve of the unit cell 16 and the fuel cell stack unit 19 according to Embodiment 2 of the present invention
  • FIG. 8 is a schematic diagram showing the structure of a solid oxide fuel cell stack prepared in Comparative Example 2
  • FIG. 8 is a current-voltage-power density curve of the unit cell 63 and the fuel cell stack unit 68 provided in Comparative Example 2 of the present invention
  • Figure 9 is a graph showing the current-voltage-power density of the unit cell 66 and the fuel cell stack unit 69 provided in Comparative Example 2 of the present invention.
  • Figure 10 is a graph showing the impedance curves of the cells 63 and the fuel cell stack unit 68 provided in Comparative Example 2 of the present invention.
  • Figure 11 is a graph showing impedance curves of a single cell 66 and a fuel cell stack unit 69 provided in Comparative Example 2 of the present invention. detailed description
  • the invention provides a high temperature resistant metal connector, comprising:
  • a perovskite coating compounded on the surface of the alloy powder coating is A perovskite coating compounded on the surface of the alloy powder coating.
  • FIG. 1 is a schematic structural view of a high temperature resistant metal connecting member according to an embodiment of the present invention, wherein 1 is a metal connecting member base, 2 is an alloy powder coating composited on the surface of the metal connecting member 1 , and 3 is a composite. A perovskite coating on the surface of the alloy powder coating 2.
  • the high temperature resistant metal connector provided by the invention has a metal connector base/alloy powder coating/4 bismuth titanium oxide coating structure, wherein the alloy powder coating can enhance the metal connector base and the perovskite coating Compatibility between the perovskite coating and the metal connector substrate, the perovskite coating is not easy to fall off, and is more suitable for use in high temperature environments, such as solids at an operating temperature of 850 ° C Used in oxide fuel cell stacks, high temperature oxidation is not easy to occur.
  • the metal connector substrate is a metal component capable of connecting, and a metal connector substrate of different materials, different shapes, and different structures may be used by those skilled in the art according to the environment in which the metal connector is used.
  • the metal connector substrate is preferably a metal connector for a solid oxide fuel cell stack, and the material thereof is preferably a ferritic alloy material, more preferably an Fe-Cr alloy; and the thickness thereof is preferably 1.0 mm. ⁇ 2.5 mm, more preferably 1.5 mm to 2 mm.
  • the alloy powder coating layer is a coating formed on the surface of the metal connecting member substrate by the alloy powder, which can enhance the compatibility of the metal connecting member substrate with the perovskite coating, thereby improving calcium.
  • the bonding force between the titanium ore coating and the metal connector substrate reduces its ohmic resistance.
  • the alloy powder is preferably a Cr-based alloy powder, more preferably an Fe-Cr alloy powder or a Ni-Cr alloy powder; the alloy powder is preferably a spherical, fluid alloy powder, the alloy
  • the particle size of the powder is preferably from 0.01 mm to 0.015 mm, and more preferably from 0.02 mm to 0.13 mm.
  • the thickness of the alloy powder coating layer is preferably 0.02 mm to 0.20 mm, more preferably 0.05 mm to 0.15 mm.
  • the resulting coating is a key part of high temperature resistance.
  • the 4 ornithose is preferably yttrium doped lanthanum manganate, cerium doped lanthanum cobaltate or lanthanum and iron doped lanthanum cobaltate, more preferably yttrium doped lanthanum manganate.
  • the perovskite is consistent with the solid oxide fuel cell cathode material.
  • the 4 ornithose is preferably a spherical, fluidity perovskite, and the particle size thereof is preferably
  • the thickness of the perovskite coating is preferably
  • the high temperature resistant metal connecting member provided by the invention can be used at 850 ° C, and the layers between the layers are tightly combined and the ohmic resistance value is low, which is particularly suitable for use as a solid oxide fuel cell stack metal connecting member.
  • the present invention also provides a method for preparing the above high temperature resistant metal connecting member, comprising the steps of: spraying a metal powder onto a surface of a metal connecting member substrate by a plasma spraying method, and forming an alloy powder layer on the metal connecting member substrate; A perovskite coating is formed on the powder layer.
  • the surface of the metal connector substrate is sprayed with an alloy powder by plasma spraying, and an alloy powder layer is formed on the metal connector substrate.
  • the alloy powder is first dried to preheat the metal connector substrate, and the preheating is preferably performed by a method of an air blasting gun or an oven preheating method, and the preheating temperature is preferably 50. °C ⁇ 250 ° C, more preferably 100 ° C ⁇ 200 ° C.
  • the metal connector substrate Before the metal connector substrate is preheated, the metal connector substrate is preferably blown with deionized water or alcohol, dried and fixed on the flat base according to a method well known to those skilled in the art to avoid Uneven coating thickness caused by misalignment or unevenness during spraying.
  • the dried alloy powder is fed into a plasma spray powder feeding device, and plasma spraying is performed under nitrogen protection.
  • plasma spraying the spraying distance and the current during spraying can be adjusted according to the composition of the metal connecting member base material and the alloy powder to obtain a suitable alloy powder layer.
  • the surface of the alloy powder layer sprayed on the metal connector substrate is rough coated.
  • plasma spraying is continued to form a perovskite coating on the surface of the alloy powder layer.
  • the perovskite powder is first dried, and then the dried perovskite powder is fed into a plasma spray powder feeding device, and a second spray is applied under nitrogen protection.
  • the perovskite powder feeding device and the alloy powder feeding device are different powder feeding devices.
  • the spraying distance and the current during spraying are adjusted according to the alloy powder composition and the perovskite powder composition to obtain a suitable perovskite coating.
  • the perovskite coating is preferably subjected to gas purging to obtain a metal connector base/alloy powder coating/4 perovskite coating. Structure of high temperature metal fittings.
  • the high temperature resistant metal connecting member provided by the invention can withstand high temperature of 850 ° C, has low ohmic resistance value, and has wide application, and is especially suitable for a solid oxide fuel cell stack.
  • the present invention also provides a solid oxide fuel cell stack, comprising: a stacked structure and a housing accommodating the stacked structure, wherein the stacked structure comprises:
  • More than two solid oxide fuel cells comprising a current collector layer, a cathode, an electrolyte layer and an anode stacked in sequence; Two adjacent solid oxide fuel cells are stacked by the high temperature resistant metal connectors described in the above technical solutions.
  • the solid oxide fuel cell stack provided by the invention is formed by connecting the solid oxide fuel cells with the current collecting layer through the above-mentioned high temperature resistant metal connecting member, because the metal connecting member has a small ohmic resistance value and the perovskite coating is not easy to fall off.
  • the solid oxide fuel cell stack has good output performance and a low attenuation rate, thereby having a high service life.
  • the solid oxide fuel cell stack provided by the present invention comprises a stacked structure, which is a structure in which a plurality of solid oxide fuel cells are connected by a metal connecting member, comprising:
  • More than two solid oxide fuel cells comprising a current collector layer, a cathode, an electrolyte layer and an anode stacked in sequence;
  • the solid oxide fuel cell includes a current collector layer, a cathode, an electrolyte layer, and an anode which are sequentially stacked, that is, the solid oxide fuel cell includes:
  • the anode of the present invention is not particularly limited, and a porous anode supporting material or an anode which is well known to those skilled in the art may be used.
  • the electrolyte layer of the present invention is not particularly limited, such as YSZ or the like.
  • the cathode of the present invention is not particularly limited, and cerium-doped lanthanum manganate, cerium-doped lanthanum cobaltate or lanthanum and iron-doped lanthanum cobaltate, and more preferably cerium-doped lanthanum manganate.
  • the current collecting layer functions to conduct current generated by the solid oxide fuel cell, and the present invention has no particular limitation on the current collecting layer, and is well known to those skilled in the art for solid oxidation.
  • the current collector layer of the fuel cell can be used.
  • the solid oxide fuel cell can be directly formed by using a commercially available solid oxide fuel cell sheet, such as a SOFC single cell produced by the Ningbo Institute of Materials Technology and Engineering of the Chinese Academy of Sciences, and being combined with the current collecting layer.
  • a stacked structure can be obtained by joining a number of solid oxide fuel cells by the high temperature resistant metal connectors described above.
  • two adjacent solid oxide fuel cells are respectively referred to as a first solid oxide fuel cell and a second solid oxide fuel cell, and the first solid oxide fuel is used by the high temperature resistant metal connecting member
  • the current collecting layer of the battery is connected to the anode of the second solid oxide fuel cell.
  • the solid oxide fuel cell stack provided by the present invention further includes a housing for accommodating the stacked structure to form a solid oxide fuel cell stack that can be used directly.
  • the present invention is not particularly limited to the housing.
  • the solid oxide fuel cell stack is operated at 850 ° C by using hydrogen as a fuel and air as an oxidant, and the output performance test and impedance performance test are performed on the solid oxide fuel cell stack, and the results show that the above high temperature resistant metal connection is adopted.
  • the output and impedance properties of a post-solid oxide fuel cell stack are essentially indistinguishable from those of a solid oxide fuel cell stack using uncoated metal connectors. It can be seen that the high temperature resistant metal connector provided by the present invention can improve the output performance of the fuel cell stack, reduce the attenuation speed, and ultimately improve the service life of the solid oxide fuel cell stack.
  • the metal connecting member substrate was purged with deionized water, dried and firmly fixed on the flat base; the metal connecting member was ground at 100 ° C Preheating; Ni-Cr alloy powder of type DG.Cr50 and particle size of 0.01mm ⁇ 0.15mm purchased from Chengdu Daguang Thermal Spraying Material Co., Ltd. is dried and sent to plasma spraying machine, under nitrogen protection The preheated metal connector substrate is sprayed to obtain a 1 mm thick alloy powder coating;
  • the LSM powder with a particle size of 0.01mm ⁇ 0.15mm is dried from the Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, and then sent to a plasma spraying machine to spray the alloy powder coating under nitrogen protection.
  • a 1 mm thick perovskite coating was formed on the surface of the powder coating to obtain a metal joint having a structure of a metal joint substrate (2 mm) / alloy powder coating (1 mm) / 4 bowelite coating (1 mm).
  • FIG. 2 is a schematic structural view of a solid oxide fuel cell stack prepared according to Embodiment 2 of the present invention, wherein 11 is the metal connecting member prepared in Embodiment 1, and 12 is the first current collecting 13 is a single cell with batch number D110113-1, 14 is the first SUS430 metal connector, 15 is the second current collector, 16 is the single cell with the batch number D110218-4, and 17 is the second SUS430 metal connection.
  • the two sides of the metal connecting member 14 and the metal connecting member 17 are respectively connected with voltage lines, and the outer sides of the metal connecting member 11 and the metal connecting member 17 are respectively connected with current lines.
  • the fuel cell stack uses hydrogen as fuel and air as oxidant.
  • the flow rates of hydrogen and air are 7 mL/cm 2 and 18 mL/cm 2 , respectively.
  • the fuel cell stack is heated from room temperature to 850 ° C after 840 min, and after 2 h of heat preservation. After pressurization, after the performance of the fuel cell stack is stabilized, the output performance tests are performed on the single cell 13, the single cell 16, the fuel cell stack unit 18, and the fuel cell stack unit 19, respectively. The results are shown in Fig. 3 and Fig. 4, Fig.
  • FIG. 3 is The current-voltage-power density curve of the unit cell 13 and the fuel cell stack unit 18 provided in the second embodiment of the present invention, wherein the curve 21 is a current-voltage curve of the unit cell 13, and the curve 22 is a current-voltage curve of the fuel cell unit 18.
  • the curve 23 is the current-power density curve of the single cell 13, and the curve 24 is the current-power density curve of the fuel cell unit 18.
  • curve 4 is the current of the cell 16 and the fuel cell stack unit 19 according to Embodiment 2 of the present invention - A voltage-power density curve, wherein curve 31 is the current-voltage curve of cell 16 , curve 32 is the current-voltage curve of fuel cell unit 19, and curve 33 is the current-power density of cell 16 Curve, curve 34 is the current-power density curve of fuel cell unit 19.
  • the output performance of the fuel cell reactor obtained by using the two-layer coated metal connector provided by the present invention is substantially consistent with the output performance of the single cell itself, and the output power density is substantially indistinguishable;
  • the output performance of the fuel cell reactor obtained by using the uncoated metal joint is substantially the same as that of the single cell itself, and the output power density is substantially indistinguishable.
  • the coating of the two-layer coated metal connector provided by the present invention has a tight interface, and the resistance caused by the coating is negligible, and does not affect the output performance and service life of the solid oxide fuel cell.
  • the single cell 13, the single cell 16, the fuel cell stack unit 18, and the fuel cell stack unit 19 are respectively subjected to impedance test.
  • FIG. 5 is an impedance curve of the unit cell 13 and the fuel cell stack unit 18 according to Embodiment 2 of the present invention.
  • the curve 41 is the impedance curve of the unit cell 13
  • the curve 42 is the impedance curve of the fuel cell unit 18.
  • FIG. 6 is the impedance curve of the unit cell 16 and the fuel cell stack unit 19 according to the embodiment 2 of the present invention, wherein the curve 51 is The impedance curve of the single cell 16 and the curve 52 are the impedance curves of the fuel cell unit 19.
  • the ohmic resistance value of the fuel cell reactor obtained by using the two-layer coated metal connecting member provided by the present invention is substantially the same as the ohmic resistance value of the single cell itself.
  • the two-coated metal connector has a small electrical resistance that substantially achieves the resistance of the uncoated metal connector, thereby indicating that the two layers of the interface are tightly bonded without increasing the electrical resistance of the metal connector.
  • the metal connector base As a metal connector base with a thickness of 2 mm, the metal connector base was purged with deionized water, dried and fixed firmly on the flat base; The substrate is sandblasted to obtain a rough surface;
  • the LSM powder with a particle size of 0.01mm ⁇ 0.15mm is dried from the Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, and then sent to a plasma spraying machine to spray the rough surface of the metal connecting member under nitrogen protection.
  • a 1 mm thick perovskite coating was formed on the surface of the metal connector substrate to obtain a metal connector having a metal connector base (2 mm) / 4 canalite coating (1 mm).
  • FIG. 7 is a schematic structural view of the solid oxide fuel cell stack prepared in Comparative Example 2 of the present invention.
  • 61 is a metal connector prepared in Comparative Example 1, 62 is a first current collector, 63 is a single cell of batch number D110114-1, 64 is a first SUS430 metal connector, and 65 is a second current collector , 66 is the production of the batch number D110114-5 single battery, 67 is a second SUS430 metal connector, 68 is a single cell 63, a current collector 62 and a metal connector 61 constitute a fuel cell stack unit, 69 is a fuel cell stack composed of a single cell 66, a current collector 65 and a metal connector 64.
  • the unit wherein the metal connector 61, the metal connector 64 and the metal connector 67 are respectively connected with voltage lines, and the metal connector 61 and the metal connector 67 are respectively connected with current lines.
  • the fuel cell stack uses hydrogen as a fuel and air as an oxidant, and the flow rates of hydrogen and air are respectively
  • FIG. 8 is a current-voltage-power of the unit cell 63 and the fuel cell stack unit 68 provided in Comparative Example 2 of the present invention.
  • the density curve wherein the curve 71 is the current-voltage curve of the single cell 63, the curve 72 is the current-voltage curve of the fuel cell unit 68, the curve 73 is the current-power density curve of the single cell 63, and the curve 74 is the fuel cell unit 68.
  • the output performance of the fuel cell reactor obtained by using the conventional metallized joint coated with the single-layer perovskite coating is greatly different from the output performance of the single cell itself, and the output power density is also different.
  • the output performance of the fuel cell reactor obtained by using the uncoated metal connector is substantially the same as that of the single cell itself, and the output power density is substantially the same. It is thus known that conventional metal connectors coated with a single layer of perovskite coating increase the interfacial contact resistance, thereby affecting the output performance and service life of the solid oxide fuel cell.
  • the single cell 63, the single cell 66, the fuel cell stack unit 68, and the fuel cell stack unit 69 are respectively subjected to impedance test, and the difference between the impedance of the single cell 63 and the fuel cell stack unit 68 is the impedance of the metal connecting member 61, and the single cell 66
  • the difference from the impedance of the fuel cell stack unit 69 is the impedance of the metal connector 64.
  • Figs. 10 and 11 are impedance curves of the unit cell 63 and the fuel cell stack unit 68 provided in Comparative Example 2 of the present invention.
  • the curve 91 is the impedance curve of the unit cell 63
  • the curve 92 is the impedance curve of the fuel cell unit 68.
  • the ohmic resistance value of the fuel cell reactor obtained by using the conventional metallized joint coated with the single-layer perovskite coating differs greatly from the ohmic resistance value of the single-cell itself, indicating that the conventional coating is coated.
  • the single-layer perovskite coated metal joint has a higher electrical resistance, indicating that the single-layer perovskite coating increases the electrical resistance of the metal joint.
  • the present invention provides a metal connector having a metal connector base/alloy powder coating/4 perovskite coating structure, a perovskite coating, an alloy powder coating, and
  • the interface between the metal connector substrates is tightly combined, and the interface resistance is not increased when used in a solid oxide fuel cell stack, thereby improving the output performance and service life of the solid oxide fuel cell stack.

Abstract

A heat-resistant metal connecting component comprises: a metal connecting component substrate; a alloy powder coating layer compounded with the surface of the metal substrate; and a perovskite coating layer compounded with the surface of the alloy powder coating layer. The heat-resistant metal connecting component is produced by plasma spraying alloy powder to the surface of the metal connector substrate, resulting in a alloy powder layer formed on the substrate, and thereafter plasma spraying perovskite powder to the surface of the alloy powder layer resulting in a perovskite layer formed on the alloy layer. The heat-resistant metal connecting component have a low ohmic resistance, and may be used in solid oxide fuel cells (SOFCs).

Description

耐高温金属连接件、 其制备方法及固体氧化物燃料电池堆 技术领域  High temperature resistant metal connector, preparation method thereof and solid oxide fuel cell stack
本发明属于固体氧化物燃料电池技术领域，尤其涉及一种耐高温金属连接 件及固体氧化物燃料电池堆。 背景技术  The invention belongs to the technical field of solid oxide fuel cells, and in particular relates to a high temperature resistant metal connector and a solid oxide fuel cell stack. Background technique
随着固体氧化物燃料电池（SOFC ) 的工作温度降低到 850°C以下， 金属 材料成为了固体氧化物燃料电池堆中连接件的首选， 尤其是铁素体合金材料， 如 Fe-16Cr、 Fe~22Cr等。 但是， Fe-Cr合金连接件在 SOFC的工作温度下会发 生高温氧化， 其表面的 Cr元素也容易挥发， 从而加速电池堆寿命的衰减。  As the operating temperature of solid oxide fuel cells (SOFC) drops below 850 °C, metallic materials are the preferred choice for connectors in solid oxide fuel cell stacks, especially ferritic alloy materials such as Fe-16Cr, Fe. ~22Cr and so on. However, Fe-Cr alloy joints undergo high temperature oxidation at the operating temperature of the SOFC, and the Cr element on the surface is also easily volatilized, thereby accelerating the decay of the life of the stack.
现有技术一般通过在连接件表面制备一层致密的高温防护涂层，以避免高 温氧化和 Cr元素的挥发。 目前主要有以下三类高温防护涂层：  The prior art generally avoids high temperature oxidation and volatilization of Cr by preparing a dense high temperature protective coating on the surface of the connector. At present, there are mainly three types of high temperature protective coatings:
( 1 ) 氮化物涂层  (1) nitride coating
氮化物涂层主要采用真空沉积 （PVD ) 方法制备得到， 包括 CrN/AlN、 Nitride coatings are mainly prepared by vacuum deposition (PVD) methods, including CrN/AlN,
Cr-Al-O-N, TiAIN和 SmCoN等。 氮化物涂层能够获得较低的金属连接件面电 阻， 有效防止高温氧化和 Cr元素挥发， 但是， 氮化物高温不稳定， 而且涂层 的制备成本高、 沉积率低， 限制了其应用。 Cr-Al-O-N, TiAIN and SmCoN, and the like. The nitride coating can obtain a lower surface resistance of the metal joint, effectively preventing high temperature oxidation and Cr element volatilization. However, the high temperature instability of the nitride, and the high preparation cost and low deposition rate of the coating limit its application.
( 2 ) 尖晶石涂层  (2) Spinel coating
尖晶石涂层具有更好的高温性能， 主要包括含 Cr尖晶石和无 Cr尖晶石。 其中，含 Cr尖晶石依然存在 Cr元素挥发的问题；无 Cr尖晶石，如 (Mn,Co)304 等则能够有效防止高温氧化和 Cr元素挥发。 但是， 尖晶石一般采用湿法涂层 后高温烧结数百小时的方法形成涂层或者先在连接件上涂层 Mn、Co等合金再 氧化后得到， 制备方法复杂、 不利于工业上大范围的推广。 The spinel coating has better high temperature properties, mainly including Cr-containing spinel and Cr-free spinel. Among them, Cr-containing spinel still has the problem of Cr element volatilization; Cr-free spinel, such as (Mn, Co) 3 4 4 , can effectively prevent high temperature oxidation and Cr element volatilization. However, the spinel is generally formed by a wet coating and then sintering at a high temperature for hundreds of hours to form a coating or a coating of a coating such as Mn or Co on a connecting member, and the preparation method is complicated and unfavorable for a wide range of industries. Promotion.
( 3 )钙钛矿涂层  (3) Perovskite coating
钙钛矿涂层结构通常为 AB03型， 其中， A为 La、 Ce、 Pr或 Nb等， B为 Co、 Mn、 Fe、 Cr、 Cu或 V等， 如 LaCr03、 LaMn03或 La(Co,Fe)03等。 钙钛 矿涂层可采用等离子喷涂、 湿法喷涂后烧结或雾化沉积等多种方法制备得到， 能够有效防止高温氧化和 Cr元素挥发， 是目前固体氧化物燃料电池堆金属连 接件最常用的涂层。 The perovskite coating structure is usually AB0 3 type, wherein A is La, Ce, Pr or Nb, etc., B is Co, Mn, Fe, Cr, Cu or V, etc., such as LaCr0 3 , LaMn0 3 or La (Co , Fe) 0 3 and so on. The perovskite coating can be prepared by various methods such as plasma spraying, wet spraying, sintering or atomization deposition, and can effectively prevent high temperature oxidation and Cr element volatilization. The most common coating for the fitting.
在金属连接件上制备 4弓钛矿涂层的方法中，等离子体喷涂法由于具有工艺 筒单、成本较低的优点而被广泛使用。在采用等离子喷涂法制备 4弓钛矿的过程 中， 首先需要对金属连接件进行喷砂等表面处理， 由于喷砂过程中需要使用 0.5MPa~0.6MPa的高压气体，容易导致金属连接件变形，影响金属连接件的使 用。 另外， 钙钛矿涂层与金属连接件表面的结合力较低， 欧姆电阻值较高， 且 在高温下容易脱落， 影响固体氧化物燃料电池堆的输出性能和使用寿命。 发明内容  In the method of preparing a 4 canalite coating on a metal joint, the plasma spray method is widely used because of its advantages of a process cartridge and a low cost. In the process of preparing 4 orthosite by plasma spraying method, firstly, the metal connecting member is subjected to surface treatment such as sand blasting. Since the high pressure gas of 0.5 MPa to 0.6 MPa is required in the blasting process, the metal connecting member is easily deformed. Affect the use of metal connectors. In addition, the perovskite coating has a low bonding force to the surface of the metal connector, has a high ohmic resistance value, and is easily detached at a high temperature, which affects the output performance and service life of the solid oxide fuel cell stack. Summary of the invention
有鉴于此， 本发明要解决的技术问题在于提供一种耐高温金属连接件、其 制备方法及固体氧化物燃料电池堆， 本发明提供的耐高温金属连接件可在 850 °C下使用， 用于固体氧化物燃料电池堆时欧姆电阻值较低。  In view of the above, the technical problem to be solved by the present invention is to provide a high temperature resistant metal connecting member, a manufacturing method thereof and a solid oxide fuel cell stack. The high temperature resistant metal connecting member provided by the present invention can be used at 850 ° C. The ohmic resistance value is lower in the solid oxide fuel cell stack.
本发明提供了一种耐高温金属连接件， 包括：  The invention provides a high temperature resistant metal connector, comprising:
金属连接件基底；  Metal connector base;
复合在所述金属连接件基底表面的合金粉体涂层；  An alloy powder coating compounded on a surface of the metal connector substrate;
复合在所述合金粉体涂层表面的钙钛矿涂层。  A perovskite coating compounded on the surface of the alloy powder coating.
优选的， 所述合金粉体涂层中的合金粉体为 Cr基合金粉体。  Preferably, the alloy powder in the alloy powder coating layer is a Cr-based alloy powder.
优选的， 所述 Cr基合金粉体为 Fe-Cr合金粉体或 Ni-Cr合金粉体。  Preferably, the Cr-based alloy powder is a Fe-Cr alloy powder or a Ni-Cr alloy powder.
优选的， 所述合金粉体涂层中的合金粉体的粒度为 0.01mm~0.15mm。 优选的， 所述合金粉体涂层的厚度为 0.02mm~0.2mm。  Preferably, the alloy powder in the alloy powder coating has a particle size of 0.01 mm to 0.15 mm. Preferably, the alloy powder coating has a thickness of 0.02 mm to 0.2 mm.
优选的， 所述 4弓钛矿涂层中的钙钛矿为锶掺杂的锰酸镧、锶掺杂的钴酸镧 或锶和铁掺杂的钴酸镧。  Preferably, the perovskite in the 4 ornithose coating is cerium-doped lanthanum manganate, cerium-doped lanthanum cobaltate or cerium and iron-doped lanthanum cobaltate.
优选的， 所述钙钛矿涂层中钙钛矿的粒度为 0.01mm~0.15mm。  Preferably, the perovskite has a particle size of 0.01 mm to 0.15 mm in the perovskite coating.
优选的， 所述钙钛矿涂层的厚度为 0.02mm~0.15mm。  Preferably, the perovskite coating has a thickness of from 0.02 mm to 0.15 mm.
本发明还提供了一种上述技术方案所述的耐高温金属连接件的制备方法， 包括以下步骤：  The invention also provides a preparation method of the high temperature resistant metal connector according to the above technical solution, comprising the following steps:
采用等离子喷涂的方法向金属连接件基底表面喷涂合金粉体，在所述金属 连接件基底上形成合金粉体层； 金粉体层上形成钙钛矿涂层。 Spraying an alloy powder onto the surface of the metal connector substrate by plasma spraying, and forming an alloy powder layer on the metal connector substrate; A perovskite coating is formed on the gold powder layer.
本发明还提供了一种固体氧化物燃料电池堆， 包括： 堆叠结构和容纳所述 堆叠结构的壳体， 其中， 所述堆叠结构包括：  The present invention also provides a solid oxide fuel cell stack, comprising: a stacked structure and a housing accommodating the stacked structure, wherein the stacked structure comprises:
两个以上固体氧化物燃料电池，所述固体氧化物燃料电池包括依次堆叠的 集流层、 阴极、 电解质层和阳极；  More than two solid oxide fuel cells comprising a current collector layer, a cathode, an electrolyte layer and an anode stacked in sequence;
相邻两个固体氧化物燃料电池通过上述技术方案所述的耐高温金属连接 件相堆叠。  Two adjacent solid oxide fuel cells are stacked by the high temperature resistant metal connectors described in the above technical solutions.
与现有技术相比，本发明提供的耐高温金属连接件包括：金属连接件基底； 复合在所述金属连接件基底表面的合金粉体涂层；复合在所述合金粉体涂层表 面的钙钛矿涂层。本发明在金属连接件基底和钙钛矿涂层之间设置了一层合金 粉体涂层， 所述合金粉体涂层能够在金属连接件基底上形成粗糙表面，从而无 需进行喷砂处理， 不会使金属连接件基底发生变形。所述合金粉体涂层能够增 强金属连接件基底与钙钛矿涂层之间的相容性，从而提高钙钛矿涂层与金属连 接件基底之间的结合力， 钙钛矿涂层不易脱落， 更适于高温环境下使用， 如在 工作温度为 850°C的固体氧化物燃料电池堆中使用， 不易发生高温氧化。  Compared with the prior art, the high temperature resistant metal connector provided by the present invention comprises: a metal connector substrate; an alloy powder coating composited on the surface of the metal connector substrate; and composited on the surface of the alloy powder coating Perovskite coating. The invention provides an alloy powder coating between the metal connector substrate and the perovskite coating, and the alloy powder coating can form a rough surface on the metal connector substrate, thereby eliminating the need for sandblasting. The metal connector substrate is not deformed. The alloy powder coating can enhance the compatibility between the metal connector substrate and the perovskite coating, thereby improving the bonding force between the perovskite coating and the metal connector substrate, and the perovskite coating is not easy. Shedding, more suitable for use in high temperature environments, such as in solid oxide fuel cell stacks operating at 850 ° C, is not prone to high temperature oxidation.
本发明提供的耐高温金属连接件可用于固体氧化物燃料电池堆，其界面结 合紧密、 欧姆电阻值低， 能够提高燃料电池堆的输出性能， 降低其衰减速度， 最终提高其使用寿命。 实验表明， 采用本发明提供的耐高温金属连接件制备的 固体氧化物燃料电池堆的输出性能、输出功率密度、欧姆电阻值等与未进行涂 层的金属连接件的相应性能基本无差别。 附图说明  The high temperature resistant metal connector provided by the invention can be used for a solid oxide fuel cell stack, and has a tight interface and a low ohmic resistance value, can improve the output performance of the fuel cell stack, reduce the attenuation speed, and ultimately improve the service life. Experiments have shown that the output performance, output power density, ohmic resistance value, etc. of the solid oxide fuel cell stack prepared by the high temperature resistant metal connecting member provided by the present invention are substantially indistinguishable from the corresponding properties of the uncoated metal connecting member. DRAWINGS
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施 例或现有技术描述中所需要使用的附图作筒单地介绍，显而易见地， 下面描述 中的附图仅仅是本发明的一些实施例， 对于本领域普通技术人员来讲，在不付 出创造性劳动的前提下， 还可以根据这些附图获得其他的附图。  In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below. Obviously, the drawings in the following description It is merely some embodiments of the present invention, and those skilled in the art can obtain other drawings according to these drawings without any creative work.
图 1为本发明实施例提供的耐高温金属连接件的结构示意图；  1 is a schematic structural view of a high temperature resistant metal connector according to an embodiment of the present invention;
图 2为本发明实施例 2制备的固体氧化物燃料电池堆的结构示意图； 图 3为本发明实施例 2提供的单电池 13和燃料电池堆单元 18的电流-电 压-功率密度曲线； 2 is a schematic structural view of a solid oxide fuel cell stack prepared according to Embodiment 2 of the present invention; FIG. 3 is a current-electrical circuit of a single cell 13 and a fuel cell stack unit 18 according to Embodiment 2 of the present invention; Pressure-power density curve;
图 4为本发明实施例 2提供的单电池 16和燃料电池堆单元 19的电流-电 压-功率密度曲线；  4 is a current-voltage-power density curve of the unit cell 16 and the fuel cell stack unit 19 according to Embodiment 2 of the present invention;
图 5为本发明实施例 2提供的单电池 13和燃料电池堆单元 18的阻抗曲线； 图 6为本发明实施例 2提供的单电池 16和燃料电池堆单元 19的阻抗曲线； 图 7为本发明比较例 2制备的固体氧化物燃料电池堆的结构示意图； 图 8为本发明比较例 2提供的单电池 63和燃料电池堆单元 68的电流-电 压-功率密度曲线；  5 is an impedance curve of the unit cell 13 and the fuel cell stack unit 18 according to Embodiment 2 of the present invention; FIG. 6 is an impedance curve of the unit cell 16 and the fuel cell stack unit 19 according to Embodiment 2 of the present invention; FIG. 8 is a schematic diagram showing the structure of a solid oxide fuel cell stack prepared in Comparative Example 2; FIG. 8 is a current-voltage-power density curve of the unit cell 63 and the fuel cell stack unit 68 provided in Comparative Example 2 of the present invention;
图 9为本发明比较例 2提供的单电池 66和燃料电池堆单元 69的电流-电 压-功率密度曲线；  Figure 9 is a graph showing the current-voltage-power density of the unit cell 66 and the fuel cell stack unit 69 provided in Comparative Example 2 of the present invention;
图 10为本发明比较例 2提供的单电池 63和燃料电池堆单元 68的阻抗曲 线；  Figure 10 is a graph showing the impedance curves of the cells 63 and the fuel cell stack unit 68 provided in Comparative Example 2 of the present invention;
图 11为本发明比较例 2提供的单电池 66和燃料电池堆单元 69的阻抗曲 线。 具体实施方式  Figure 11 is a graph showing impedance curves of a single cell 66 and a fuel cell stack unit 69 provided in Comparative Example 2 of the present invention. detailed description
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清 楚、 完整地描述， 显然， 所描述的实施例仅仅是本发明一部分实施例， 而不是 全部的实施例。基于本发明中的实施例， 本领域普通技术人员在没有做出创造 性劳动前提下所获得的所有其他实施例， 都属于本发明保护的范围。  BRIEF DESCRIPTION OF THE DRAWINGS The technical solutions in the embodiments of the present invention will be described in detail below with reference to the accompanying drawings. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without the creative work are all within the scope of the present invention.
本发明提供了一种耐高温金属连接件， 包括：  The invention provides a high temperature resistant metal connector, comprising:
金属连接件基底；  Metal connector base;
复合在所述金属连接件基底表面的合金粉体涂层；  An alloy powder coating compounded on a surface of the metal connector substrate;
复合在所述合金粉体涂层表面的钙钛矿涂层。  A perovskite coating compounded on the surface of the alloy powder coating.
参见图 1 , 图 1为本发明实施例提供的耐高温金属连接件的结构示意图， 其中， 1为金属连接件基底， 2为复合在金属连接件 1表面的合金粉体涂层， 3 为复合在合金粉体涂层 2表面的钙钛矿涂层。  Referring to FIG. 1 , FIG. 1 is a schematic structural view of a high temperature resistant metal connecting member according to an embodiment of the present invention, wherein 1 is a metal connecting member base, 2 is an alloy powder coating composited on the surface of the metal connecting member 1 , and 3 is a composite. A perovskite coating on the surface of the alloy powder coating 2.
本发明提供的耐高温金属连接件具有金属连接件基底 /合金粉体涂层 /4丐钛 矿涂层的结构， 其中，合金粉体涂层能够增强金属连接件基底与钙钛矿涂层之 间的相容性，从而提高钙钛矿涂层与金属连接件基底之间的结合力，钙钛矿涂 层不易脱落， 更适于高温环境下使用， 如在工作温度为 850°C的固体氧化物燃 料电池堆中使用， 不易发生高温氧化。 The high temperature resistant metal connector provided by the invention has a metal connector base/alloy powder coating/4 bismuth titanium oxide coating structure, wherein the alloy powder coating can enhance the metal connector base and the perovskite coating Compatibility between the perovskite coating and the metal connector substrate, the perovskite coating is not easy to fall off, and is more suitable for use in high temperature environments, such as solids at an operating temperature of 850 ° C Used in oxide fuel cell stacks, high temperature oxidation is not easy to occur.
在本发明中， 所述金属连接件基底为能够起连接作用的金属部件， 本领域 技术人员可以根据该金属连接件的使用环境采用不同材质、 不同形状、 不同结 构的金属连接件基底。在本发明中， 所述金属连接件基底优选为用于固体氧化 物燃料电池堆的金属连接件， 其材质优选为铁素体合金材料， 更优选为 Fe-Cr 合金； 其厚度优选为 1.0mm~2.5mm, 更优选为 1.5mm~2mm。  In the present invention, the metal connector substrate is a metal component capable of connecting, and a metal connector substrate of different materials, different shapes, and different structures may be used by those skilled in the art according to the environment in which the metal connector is used. In the present invention, the metal connector substrate is preferably a metal connector for a solid oxide fuel cell stack, and the material thereof is preferably a ferritic alloy material, more preferably an Fe-Cr alloy; and the thickness thereof is preferably 1.0 mm. ~2.5 mm, more preferably 1.5 mm to 2 mm.
在本发明中，所述合金粉体涂层为由合金粉体在所述金属连接件基底表面 形成的涂层， 能够增强金属连接件基底与钙钛矿涂层的相容性，从而提高钙钛 矿涂层与金属连接件基底之间的结合力， 降低其欧姆电阻值。所述合金粉体优 选为 Cr基合金粉体， 更优选为 Fe-Cr合金粉体或 Ni-Cr合金粉体； 所述合金 粉体优选为球形、 流动性好的合金粉体， 所述合金粉体的粒度优选为 0.01mm~0.015mm, 更优选为 0.02mm~0.13mm。所述合金粉体涂层的厚度优选 为 0.02mm~0.20mm, 更优选为 0.05mm~0.15mm。 成的涂层， 是耐高温的关键部分。 所述 4弓钛矿优选为锶掺杂的锰酸镧、 锶掺杂 的钴酸镧或锶和铁掺杂的钴酸镧， 更优选为锶掺杂的锰酸镧。 当所述耐高温金 属连接件用于固体氧化物燃料电池堆时，所述钙钛矿与所述固体氧化物燃料电 池阴极材料一致。 所述 4弓钛矿优选为球形、 流动性好的钙钛矿， 其粒度优选为 In the present invention, the alloy powder coating layer is a coating formed on the surface of the metal connecting member substrate by the alloy powder, which can enhance the compatibility of the metal connecting member substrate with the perovskite coating, thereby improving calcium. The bonding force between the titanium ore coating and the metal connector substrate reduces its ohmic resistance. The alloy powder is preferably a Cr-based alloy powder, more preferably an Fe-Cr alloy powder or a Ni-Cr alloy powder; the alloy powder is preferably a spherical, fluid alloy powder, the alloy The particle size of the powder is preferably from 0.01 mm to 0.015 mm, and more preferably from 0.02 mm to 0.13 mm. The thickness of the alloy powder coating layer is preferably 0.02 mm to 0.20 mm, more preferably 0.05 mm to 0.15 mm. The resulting coating is a key part of high temperature resistance. The 4 ornithose is preferably yttrium doped lanthanum manganate, cerium doped lanthanum cobaltate or lanthanum and iron doped lanthanum cobaltate, more preferably yttrium doped lanthanum manganate. When the refractory metal link is used in a solid oxide fuel cell stack, the perovskite is consistent with the solid oxide fuel cell cathode material. The 4 ornithose is preferably a spherical, fluidity perovskite, and the particle size thereof is preferably
0.01mm~0.015mm, 更优选为 0.02mm~0.13mm。所述钙钛矿涂层的厚度优选为From 0.01 mm to 0.015 mm, more preferably from 0.02 mm to 0.13 mm. The thickness of the perovskite coating is preferably
0.02mm~0.20mm, 更优选为 0.05mm~0.15mm。 0.02 mm to 0.20 mm, more preferably 0.05 mm to 0.15 mm.
本发明提供的耐高温金属连接件可在 850°C下使用， 其各层之间结合紧 密， 欧姆电阻值低， 特别适合用作固体氧化物燃料电池堆金属连接件。  The high temperature resistant metal connecting member provided by the invention can be used at 850 ° C, and the layers between the layers are tightly combined and the ohmic resistance value is low, which is particularly suitable for use as a solid oxide fuel cell stack metal connecting member.
本发明还提供了上述耐高温金属连接件的制备方法， 包括以下步骤： 采用等离子喷涂的方法向金属连接件基底表面喷涂合金粉体，在所述金属 连接件基底上形成合金粉体层； 金粉体层上形成钙钛矿涂层。 首先采用等离子喷涂的方法向金属连接件基底表面喷涂合金粉体，在所述 金属连接件基底上形成合金粉体层。在进行喷涂前，首先将所述合金粉体烘干， 将所述金属连接件基底进行预热，所述预热优选采用空走喷枪的方法或者烘箱 预热的方法， 预热温度优选为 50°C ~250°C , 更优选为 100°C ~200°C。 The present invention also provides a method for preparing the above high temperature resistant metal connecting member, comprising the steps of: spraying a metal powder onto a surface of a metal connecting member substrate by a plasma spraying method, and forming an alloy powder layer on the metal connecting member substrate; A perovskite coating is formed on the powder layer. First, the surface of the metal connector substrate is sprayed with an alloy powder by plasma spraying, and an alloy powder layer is formed on the metal connector substrate. Before the spraying, the alloy powder is first dried to preheat the metal connector substrate, and the preheating is preferably performed by a method of an air blasting gun or an oven preheating method, and the preheating temperature is preferably 50. °C ~ 250 ° C, more preferably 100 ° C ~ 200 ° C.
在将所述金属连接件基底进行预热之前，优选采用去离子水或酒精对所述 金属连接件基底进行吹洗，按照本领域技术人员熟知的方法干燥后牢固固定于 平整底座上， 以避免喷涂时错位或高低不平引起的涂层厚度不均匀。  Before the metal connector substrate is preheated, the metal connector substrate is preferably blown with deionized water or alcohol, dried and fixed on the flat base according to a method well known to those skilled in the art to avoid Uneven coating thickness caused by misalignment or unevenness during spraying.
将所述金属连接件基底预热后，将烘干的合金粉体送入等离子喷涂送粉装 置内， 在氮气保护下进行等离子喷涂。 在进行等离子喷涂时， 所述喷涂距离和 喷涂时的电流可以根据金属连接件基底材料、合金粉体的组成进行调节， 以便 得到合适的合金粉体层。  After the metal connector substrate is preheated, the dried alloy powder is fed into a plasma spray powder feeding device, and plasma spraying is performed under nitrogen protection. In plasma spraying, the spraying distance and the current during spraying can be adjusted according to the composition of the metal connecting member base material and the alloy powder to obtain a suitable alloy powder layer.
按照本发明， 在所述金属连接件基底上喷涂的合金粉体层表面粗糙的涂 层。  According to the present invention, the surface of the alloy powder layer sprayed on the metal connector substrate is rough coated.
在所述金属连接件基底表面形成合金粉体涂层后， 继续进行等离子喷涂， 在所述合金粉体层表面形成钙钛矿涂层。 首先将钙钛矿粉体进行干燥， 然后将 所述干燥的钙钛矿粉体送入等离子喷涂送粉装置内，在氮气保护下进行第二次 喷涂。  After forming an alloy powder coating on the surface of the metal connector substrate, plasma spraying is continued to form a perovskite coating on the surface of the alloy powder layer. The perovskite powder is first dried, and then the dried perovskite powder is fed into a plasma spray powder feeding device, and a second spray is applied under nitrogen protection.
为避免交叉污染，所述钙钛矿粉体送粉装置与所述合金粉体送粉装置为不 同的送粉装置。在进行 4丐钛矿粉体喷涂时， 所述喷涂距离和喷涂时的电流根据 合金粉体成分和钙钛矿粉体成分进行调节， 以便得到合适的钙钛矿涂层。  In order to avoid cross-contamination, the perovskite powder feeding device and the alloy powder feeding device are different powder feeding devices. In the case of 4 丐 titanium ore powder spraying, the spraying distance and the current during spraying are adjusted according to the alloy powder composition and the perovskite powder composition to obtain a suitable perovskite coating.
在所述合金粉体涂层上形成钙钛矿涂层后，优选对所述钙钛矿涂层进行气 体吹洗， 得到具有金属连接件基底 /合金粉体涂层 /4弓钛矿涂层结构的耐高温金 属连接件。  After forming a perovskite coating on the alloy powder coating, the perovskite coating is preferably subjected to gas purging to obtain a metal connector base/alloy powder coating/4 perovskite coating. Structure of high temperature metal fittings.
本发明提供的耐高温金属连接件可耐 850°C高温， 具有较低的欧姆电阻 值， 具有广泛的用途， 尤其适用于固体氧化物燃料电池堆。  The high temperature resistant metal connecting member provided by the invention can withstand high temperature of 850 ° C, has low ohmic resistance value, and has wide application, and is especially suitable for a solid oxide fuel cell stack.
本发明还提供了一种固体氧化物燃料电池堆， 包括： 堆叠结构和容纳所述 堆叠结构的壳体， 其中， 所述堆叠结构包括：  The present invention also provides a solid oxide fuel cell stack, comprising: a stacked structure and a housing accommodating the stacked structure, wherein the stacked structure comprises:
两个以上固体氧化物燃料电池，所述固体氧化物燃料电池包括依次堆叠的 集流层、 阴极、 电解质层和阳极； 相邻两个固体氧化物燃料电池通过上述技术方案所述的耐高温金属连接 件相堆叠。 More than two solid oxide fuel cells comprising a current collector layer, a cathode, an electrolyte layer and an anode stacked in sequence; Two adjacent solid oxide fuel cells are stacked by the high temperature resistant metal connectors described in the above technical solutions.
本发明提供的固体氧化物燃料电池堆由具有集流层的固体氧化物燃料电 池通过上述耐高温金属连接件连接而成， 由于采用的金属连接件欧姆电阻值 小、钙钛矿涂层不易脱落， 所述固体氧化物燃料电池堆具有良好的输出性能和 较低的衰减速率， 从而具有较高的使用寿命。  The solid oxide fuel cell stack provided by the invention is formed by connecting the solid oxide fuel cells with the current collecting layer through the above-mentioned high temperature resistant metal connecting member, because the metal connecting member has a small ohmic resistance value and the perovskite coating is not easy to fall off. The solid oxide fuel cell stack has good output performance and a low attenuation rate, thereby having a high service life.
本发明提供的固体氧化物燃料电池堆包括堆叠结构，所述堆叠结构为若干 固体氧化物燃料电池通过金属连接件连接形成的结构， 包括：  The solid oxide fuel cell stack provided by the present invention comprises a stacked structure, which is a structure in which a plurality of solid oxide fuel cells are connected by a metal connecting member, comprising:
两个以上固体氧化物燃料电池，所述固体氧化物燃料电池包括依次堆叠的 集流层、 阴极、 电解质层和阳极；  More than two solid oxide fuel cells comprising a current collector layer, a cathode, an electrolyte layer and an anode stacked in sequence;
相邻两个固体氧化物燃料电池通过上述技术方案所述的耐高温金属连接 件相堆叠。  Two adjacent solid oxide fuel cells are stacked by the high temperature resistant metal connectors described in the above technical solutions.
所述固体氧化物燃料电池包括依次堆叠的集流层、阴极、电解质层和阳极， 即所述固体氧化物燃料电池包括：  The solid oxide fuel cell includes a current collector layer, a cathode, an electrolyte layer, and an anode which are sequentially stacked, that is, the solid oxide fuel cell includes:
阳极；  Anode
与所述阳极相接触的电解质层；  An electrolyte layer in contact with the anode;
与所述电解质层相接触的阴极；  a cathode in contact with the electrolyte layer;
与所述阴极相接触的集流层。  a current collecting layer in contact with the cathode.
本发明对所述阳极没有特殊限制，本领域技术人员熟知的多孔阳极支撑材 料或者阳极均可。  The anode of the present invention is not particularly limited, and a porous anode supporting material or an anode which is well known to those skilled in the art may be used.
本发明对所述电解质层没有特殊限制， 如 YSZ等。  The electrolyte layer of the present invention is not particularly limited, such as YSZ or the like.
本发明对所述阴极没有特殊限制，锶掺杂的锰酸镧、锶掺杂的钴酸镧或锶 和铁掺杂的钴酸镧， 更优选为锶掺杂的锰酸镧等均可。  The cathode of the present invention is not particularly limited, and cerium-doped lanthanum manganate, cerium-doped lanthanum cobaltate or lanthanum and iron-doped lanthanum cobaltate, and more preferably cerium-doped lanthanum manganate.
在本发明中，所述集流层的作用在于将所述固体氧化物燃料电池产生的电 流进行传导， 本发明对所述集流层没有特殊限制， 本领域技术人员熟知的、 用 于固体氧化物燃料电池的集流层即可。  In the present invention, the current collecting layer functions to conduct current generated by the solid oxide fuel cell, and the present invention has no particular limitation on the current collecting layer, and is well known to those skilled in the art for solid oxidation. The current collector layer of the fuel cell can be used.
在本发明，所述固体氧化物燃料电池可以直接使用市场上购买的固体氧化 物燃料电池片，如中国科学院宁波材料技术与工程研究所生产的 SOFC单电池 等， 与集流层复合后形成。 将若干固体氧化物燃料电池通过上文所述的耐高温金属连接件连接后即 可得到堆叠结构。在所述堆叠结构中，相邻两个固体氧化物燃料电池分别记为 第一固体氧化物燃料电池和第二固体氧化物燃料电池，采用所述耐高温金属连 接件将第一固体氧化物燃料电池的集流层与第二固体氧化物燃料电池的阳极 相连接。 In the present invention, the solid oxide fuel cell can be directly formed by using a commercially available solid oxide fuel cell sheet, such as a SOFC single cell produced by the Ningbo Institute of Materials Technology and Engineering of the Chinese Academy of Sciences, and being combined with the current collecting layer. A stacked structure can be obtained by joining a number of solid oxide fuel cells by the high temperature resistant metal connectors described above. In the stacked structure, two adjacent solid oxide fuel cells are respectively referred to as a first solid oxide fuel cell and a second solid oxide fuel cell, and the first solid oxide fuel is used by the high temperature resistant metal connecting member The current collecting layer of the battery is connected to the anode of the second solid oxide fuel cell.
本发明提供的固体氧化物燃料电池堆还包括壳体，所述壳体用于容纳所述 堆叠结构， 形成可直接使用的固体氧化物燃料电池堆。本发明对所述壳体没有 特殊限制。  The solid oxide fuel cell stack provided by the present invention further includes a housing for accommodating the stacked structure to form a solid oxide fuel cell stack that can be used directly. The present invention is not particularly limited to the housing.
以氢气为燃料、 空气为氧化剂使所述固体氧化物燃料电池堆在 850°C下工 作，对所述固体氧化燃料电池堆进行输出性能测试和阻抗性能测试，结果表明， 采用上述耐高温金属连接件后固体氧化物燃料电池堆的输出性能和阻抗性能 与采用未涂层的金属连接件的固体氧化物燃料电池堆的性能基本无差别。由此 可见， 本发明提供的耐高温金属连接件用于固体氧化物燃料电池堆时， 能够提 高燃料电池堆的输出性能， 降低其衰减速度， 最终提高其使用寿命。  The solid oxide fuel cell stack is operated at 850 ° C by using hydrogen as a fuel and air as an oxidant, and the output performance test and impedance performance test are performed on the solid oxide fuel cell stack, and the results show that the above high temperature resistant metal connection is adopted. The output and impedance properties of a post-solid oxide fuel cell stack are essentially indistinguishable from those of a solid oxide fuel cell stack using uncoated metal connectors. It can be seen that the high temperature resistant metal connector provided by the present invention can improve the output performance of the fuel cell stack, reduce the attenuation speed, and ultimately improve the service life of the solid oxide fuel cell stack.
为了进一步说明本发明，以下结合实施例对本发明提供的耐高温金属连接 件、 其制备方法及固体氧化物燃料电池堆进行详细描述。  In order to further illustrate the present invention, the high temperature resistant metal joint provided by the present invention, a method for preparing the same, and a solid oxide fuel cell stack are described in detail below with reference to the examples.
实施例 1  Example 1
以厚度为 2mm的 SUS430金属连接件作为金属连接件基底， 用去离子水 将所述金属连接件基底吹洗干净， 干燥后牢固固定于平整底座上； 将所述金属 连接件基底在 100°C下预热； 将购自成都大光热喷涂材料有限公司的、 型号为 DG.Cr50、粒度为 0.01mm~0.15mm的 Ni-Cr合金粉末烘干后送入等离子喷涂机， 在氮气保护下对所述预热后的金属连接件基底进行喷涂， 得到 1mm厚的合金 粉末涂层；  Using a SUS430 metal connecting member with a thickness of 2 mm as a metal connecting member substrate, the metal connecting member substrate was purged with deionized water, dried and firmly fixed on the flat base; the metal connecting member was ground at 100 ° C Preheating; Ni-Cr alloy powder of type DG.Cr50 and particle size of 0.01mm~0.15mm purchased from Chengdu Daguang Thermal Spraying Material Co., Ltd. is dried and sent to plasma spraying machine, under nitrogen protection The preheated metal connector substrate is sprayed to obtain a 1 mm thick alloy powder coating;
将购自中国科学院宁波材料技术与工程研究所、 粒度为 0.01mm~0.15mm 的 LSM粉体烘干后送入等离子喷涂机， 在氮气保护下对所述合金粉体涂层进 行喷涂， 在合金粉体涂层表面形成 lmm厚的钙钛矿涂层， 得到结构为金属连 接件基底（ 2mm ) /合金粉体涂层（ lmm ) /4弓钛矿涂层（ lmm )的金属连接件。  The LSM powder with a particle size of 0.01mm~0.15mm is dried from the Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, and then sent to a plasma spraying machine to spray the alloy powder coating under nitrogen protection. A 1 mm thick perovskite coating was formed on the surface of the powder coating to obtain a metal joint having a structure of a metal joint substrate (2 mm) / alloy powder coating (1 mm) / 4 bowelite coating (1 mm).
实施例 2  Example 2
以两个集流器、中国科学院宁波材料技术与工程研究所研发的生产批号分 别为 D110113-1和 D110218-4的两个阳极支撑 Ni-YSZ/YSZ/LSM单电池、 两 个厚度为 2mm的 SUS430金属连接件和实施例 1制备的金属连接件为原料， 按照图 2所示的结构组装得到两单元燃料电池堆；图 2为本发明实施例 2制备 的固体氧化物燃料电池堆的结构示意图， 其中， 11 为实施例 1制备的金属连 接件， 12为第一集流器， 13 为生产批号为 D110113-1 的单电池， 14为第一 SUS430金属连接件， 15为第二集流器，16为生产批号为 D110218-4的单电池， 17为第二 SUS430金属连接件， 18为单电池 13、 集流器 12和金属连接件 11 组成燃料电池堆单元， 19为单电池 16、 集流器 15和金属连接件 14组成的燃 料电池堆单元， 其中， 金属连接件 11、 金属连接件 14和金属连接件 17的两 侧分别接有电压线， 金属连接件 11和金属连接件 17的外侧分别接有电流线。 Production batch number developed by two current collectors, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences Two anode-supported Ni-YSZ/YSZ/LSM single cells of D110113-1 and D110218-4, two SUS430 metal connectors of 2 mm thickness and the metal connectors prepared in Example 1 are used as raw materials, according to Figure 2 The structure shown is assembled to obtain a two-unit fuel cell stack; FIG. 2 is a schematic structural view of a solid oxide fuel cell stack prepared according to Embodiment 2 of the present invention, wherein 11 is the metal connecting member prepared in Embodiment 1, and 12 is the first current collecting 13 is a single cell with batch number D110113-1, 14 is the first SUS430 metal connector, 15 is the second current collector, 16 is the single cell with the batch number D110218-4, and 17 is the second SUS430 metal connection. a fuel cell stack unit composed of a single cell 13, a current collector 12 and a metal connecting member 11, and a fuel cell stack unit composed of a single cell 16, a current collector 15 and a metal connecting member 14, wherein the metal connecting member 11. The two sides of the metal connecting member 14 and the metal connecting member 17 are respectively connected with voltage lines, and the outer sides of the metal connecting member 11 and the metal connecting member 17 are respectively connected with current lines.
所述燃料电池堆以氢气为燃料、 空气为氧化剂， 氢气和空气的流量分别为 7mL/cm2和 18mL/cm2, 将所述燃料电池堆由室温经过 840min升温至 850°C , 保温 2h后加压，待燃料电池堆性能达到稳定后，分别对单电池 13、单电池 16、 燃料电池堆单元 18和燃料电池堆单元 19进行输出性能测试， 结果参见图 3 和图 4, 图 3为本发明实施例 2提供的单电池 13和燃料电池堆单元 18的电流 -电压-功率密度曲线， 其中， 曲线 21为单电池 13的电流 -电压曲线， 曲线 22 为燃料电池单元 18的电流 -电压曲线， 曲线 23为单电池 13的电流-功率密度 曲线， 曲线 24为燃料电池单元 18的电流-功率密度曲线； 图 4为本发明实施 例 2提供的单电池 16和燃料电池堆单元 19的电流-电压-功率密度曲线，其中， 曲线 31为单电池 16的电流 -电压曲线， 曲线 32为燃料电池单元 19的电流-电 压曲线， 曲线 33为单电池 16的电流-功率密度曲线， 曲线 34为燃料电池单元 19的电流-功率密度曲线。 The fuel cell stack uses hydrogen as fuel and air as oxidant. The flow rates of hydrogen and air are 7 mL/cm 2 and 18 mL/cm 2 , respectively. The fuel cell stack is heated from room temperature to 850 ° C after 840 min, and after 2 h of heat preservation. After pressurization, after the performance of the fuel cell stack is stabilized, the output performance tests are performed on the single cell 13, the single cell 16, the fuel cell stack unit 18, and the fuel cell stack unit 19, respectively. The results are shown in Fig. 3 and Fig. 4, Fig. 3 is The current-voltage-power density curve of the unit cell 13 and the fuel cell stack unit 18 provided in the second embodiment of the present invention, wherein the curve 21 is a current-voltage curve of the unit cell 13, and the curve 22 is a current-voltage curve of the fuel cell unit 18. The curve 23 is the current-power density curve of the single cell 13, and the curve 24 is the current-power density curve of the fuel cell unit 18. FIG. 4 is the current of the cell 16 and the fuel cell stack unit 19 according to Embodiment 2 of the present invention - A voltage-power density curve, wherein curve 31 is the current-voltage curve of cell 16 , curve 32 is the current-voltage curve of fuel cell unit 19, and curve 33 is the current-power density of cell 16 Curve, curve 34 is the current-power density curve of fuel cell unit 19.
由图 3和图 4可知，采用本发明提供的涂有两层涂层的金属连接件得到的 燃料电池反应堆的输出性能与单电池本身的输出性能基本一致，且输出功率密 度也基本无差别；采用未进行涂层的金属连接件得到的燃料电池反应堆的输出 性能与单电池本身的输出性能基本一致，且输出功率密度基本无差别。 由此可 知， 本发明提供的涂有两层涂层的金属连接件中涂层界面结合紧密， 其引起的 电阻可忽略不计， 不会对固体氧化物燃料电池的输出性能和使用寿命造成影 响。 分别对单电池 13、 单电池 16、 燃料电池堆单元 18和燃料电池堆单元 19 进行阻抗测试， 单电池 13与燃料电池堆单元 18的阻抗之差即为金属连接件 11的阻抗， 单电池 16与燃料电池堆单元 19的阻抗之差即为金属连接件 14的 阻抗， 结果参见图 5和图 6, 图 5为本发明实施例 2提供的单电池 13和燃料 电池堆单元 18的阻抗曲线， 其中曲线 41为单电池 13的阻抗曲线， 曲线 42 为燃料电池单元 18的阻抗曲线；图 6为本发明实施例 2提供的单电池 16和燃 料电池堆单元 19的阻抗曲线， 其中， 曲线 51为单电池 16的阻抗曲线， 曲线 52为燃料电池单元 19的阻抗曲线。 It can be seen from FIG. 3 and FIG. 4 that the output performance of the fuel cell reactor obtained by using the two-layer coated metal connector provided by the present invention is substantially consistent with the output performance of the single cell itself, and the output power density is substantially indistinguishable; The output performance of the fuel cell reactor obtained by using the uncoated metal joint is substantially the same as that of the single cell itself, and the output power density is substantially indistinguishable. It can be seen that the coating of the two-layer coated metal connector provided by the present invention has a tight interface, and the resistance caused by the coating is negligible, and does not affect the output performance and service life of the solid oxide fuel cell. The single cell 13, the single cell 16, the fuel cell stack unit 18, and the fuel cell stack unit 19 are respectively subjected to impedance test. The difference between the impedance of the cell 13 and the fuel cell stack unit 18 is the impedance of the metal connector 11, and the cell 16 The difference from the impedance of the fuel cell stack unit 19 is the impedance of the metal connector 14, and the results are shown in FIG. 5 and FIG. 6. FIG. 5 is an impedance curve of the unit cell 13 and the fuel cell stack unit 18 according to Embodiment 2 of the present invention. The curve 41 is the impedance curve of the unit cell 13, and the curve 42 is the impedance curve of the fuel cell unit 18. FIG. 6 is the impedance curve of the unit cell 16 and the fuel cell stack unit 19 according to the embodiment 2 of the present invention, wherein the curve 51 is The impedance curve of the single cell 16 and the curve 52 are the impedance curves of the fuel cell unit 19.
由图 5和图 6可知，采用本发明提供的涂有两层涂层的金属连接件得到的 燃料电池反应堆的欧姆电阻值与单电池本身的欧姆电阻值基本无差另 'h说明本 发明提供的涂有两层涂层的金属连接件的电阻很小，基本可达到没有涂层的金 属连接件的电阻值，从而说明该两层涂层界面结合紧密， 并未增加金属连接件 的电阻。  It can be seen from FIG. 5 and FIG. 6 that the ohmic resistance value of the fuel cell reactor obtained by using the two-layer coated metal connecting member provided by the present invention is substantially the same as the ohmic resistance value of the single cell itself. The two-coated metal connector has a small electrical resistance that substantially achieves the resistance of the uncoated metal connector, thereby indicating that the two layers of the interface are tightly bonded without increasing the electrical resistance of the metal connector.
比较例 1  Comparative example 1
以厚度为 2mm的 SUS430金属连接件作为金属连接件基底， 用去离子水 将所述金属连接件基底吹洗干净， 干燥后牢固固定于平整底座上； 在 0.5MPa 的压力下对所述金属连接件基底进行喷砂处理， 得到粗糙表面；  As a metal connector base with a thickness of 2 mm, the metal connector base was purged with deionized water, dried and fixed firmly on the flat base; The substrate is sandblasted to obtain a rough surface;
将购自中国科学院宁波材料技术与工程研究所、 粒度为 0.01mm~0.15mm 的 LSM粉体烘干后送入等离子喷涂机， 在氮气保护下对所述金属连接件基底 的粗糙表面进行喷涂， 在金属连接件基底表面形成 lmm厚的钙钛矿涂层， 得 到结构为金属连接件基底 ( 2mm ) /4弓钛矿涂层（lmm ) 的金属连接件。  The LSM powder with a particle size of 0.01mm~0.15mm is dried from the Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, and then sent to a plasma spraying machine to spray the rough surface of the metal connecting member under nitrogen protection. A 1 mm thick perovskite coating was formed on the surface of the metal connector substrate to obtain a metal connector having a metal connector base (2 mm) / 4 canalite coating (1 mm).
比较例 2  Comparative example 2
以两个集流器、中国科学院宁波材料技术与工程研究所研发的生产批号分 别为 D110114-1和 D110114-5的两个阳极支撑 Ni-YSZ/YSZ/LSM单电池、 两 个厚度为 2mm的 SUS430金属连接件和比较例 1制备的金属连接件为原料， 按照图 7所示的结构组装得到两单元燃料电池堆；图 7为本发明比较例 2制备 的固体氧化物燃料电池堆的结构示意图， 其中， 61为比较例 1制备的金属连 接件， 62为第一集流器， 63 为生产批号为 D110114-1 的单电池， 64为第一 SUS430金属连接件， 65为第二集流器，66为生产批号为 D110114-5的单电池， 67为第二 SUS430金属连接件， 68为单电池 63、 集流器 62和金属连接件 61 组成燃料电池堆单元， 69为单电池 66、 集流器 65和金属连接件 64组成的燃 料电池堆单元， 其中， 金属连接件 61、 金属连接件 64和金属连接件 67的两 侧分别接有电压线， 金属连接件 61和金属连接件 67的外侧分别接有电流线。 Two anode-supported Ni-YSZ/YSZ/LSM single cells with two batches, D110114-1 and D110114-5, developed by the Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, two thicknesses of 2mm The SUS430 metal connector and the metal connector prepared in Comparative Example 1 were used as raw materials, and the two-unit fuel cell stack was assembled according to the structure shown in FIG. 7. FIG. 7 is a schematic structural view of the solid oxide fuel cell stack prepared in Comparative Example 2 of the present invention. 61 is a metal connector prepared in Comparative Example 1, 62 is a first current collector, 63 is a single cell of batch number D110114-1, 64 is a first SUS430 metal connector, and 65 is a second current collector , 66 is the production of the batch number D110114-5 single battery, 67 is a second SUS430 metal connector, 68 is a single cell 63, a current collector 62 and a metal connector 61 constitute a fuel cell stack unit, 69 is a fuel cell stack composed of a single cell 66, a current collector 65 and a metal connector 64. The unit, wherein the metal connector 61, the metal connector 64 and the metal connector 67 are respectively connected with voltage lines, and the metal connector 61 and the metal connector 67 are respectively connected with current lines.
所述燃料电池堆以氢气为燃料、 空气为氧化剂， 氢气和空气的流量分别为 The fuel cell stack uses hydrogen as a fuel and air as an oxidant, and the flow rates of hydrogen and air are respectively
7mL/cm2和 18mL/cm2, 将所述燃料电池堆由室温经过 840min升温至 850°C , 保温 2h后加压，待燃料电池堆性能达到稳定后，分别对单电池 63、单电池 66、 燃料电池堆单元 68和燃料电池堆单元 69进行输出性能测试， 结果参见图 8 和图 9, 图 8为本发明比较例 2提供的单电池 63和燃料电池堆单元 68的电流 -电压-功率密度曲线， 其中， 曲线 71为单电池 63的电流 -电压曲线， 曲线 72 为燃料电池单元 68的电流 -电压曲线， 曲线 73为单电池 63的电流-功率密度 曲线， 曲线 74为燃料电池单元 68的电流-功率密度曲线； 图 9为本发明比较 例 2提供的单电池 66和燃料电池堆单元 69的电流-电压-功率密度曲线，其中， 曲线 81为单电池 66的电流 -电压曲线， 曲线 82为燃料电池单元 89的电流-电 压曲线， 曲线 83为单电池 66的电流-功率密度曲线， 曲线 84为燃料电池单元 69的电流 -功率密度曲线。 7mL/cm 2 and 18mL/cm 2 , the fuel cell stack is heated from room temperature to 850 ° C after 840 min, and after 2 h of heat preservation, after the performance of the fuel cell stack is stabilized, respectively, the single cell 63 and the single cell 66 are respectively The fuel cell stack unit 68 and the fuel cell stack unit 69 perform output performance tests. The results are shown in FIG. 8 and FIG. 9. FIG. 8 is a current-voltage-power of the unit cell 63 and the fuel cell stack unit 68 provided in Comparative Example 2 of the present invention. The density curve, wherein the curve 71 is the current-voltage curve of the single cell 63, the curve 72 is the current-voltage curve of the fuel cell unit 68, the curve 73 is the current-power density curve of the single cell 63, and the curve 74 is the fuel cell unit 68. The current-voltage-power density curve of the unit cell 66 and the fuel cell stack unit 69 provided in Comparative Example 2 of the present invention, wherein the curve 81 is a current-voltage curve of the unit cell 66, a curve 82 is the current-voltage curve of the fuel cell unit 89, curve 83 is the current-power density curve of the cell 66, and curve 84 is the current-power density curve of the fuel cell unit 69.
由图 8和图 9可知，采用常规的涂有单层钙钛矿涂层的金属连接件得到的 燃料电池反应堆的输出性能与单电池本身的输出性能相差较大，且输出功率密 度相差也较大；而采用未进行涂层的金属连接件得到的燃料电池反应堆的输出 性能与单电池本身的输出性能基本一致，且输出功率密度基本无差别。 由此可 知， 常规的涂有单层钙钛矿涂层的金属连接件会增加界面接触电阻，从而对固 体氧化物燃料电池的输出性能和使用寿命造成影响。  It can be seen from FIG. 8 and FIG. 9 that the output performance of the fuel cell reactor obtained by using the conventional metallized joint coated with the single-layer perovskite coating is greatly different from the output performance of the single cell itself, and the output power density is also different. The output performance of the fuel cell reactor obtained by using the uncoated metal connector is substantially the same as that of the single cell itself, and the output power density is substantially the same. It is thus known that conventional metal connectors coated with a single layer of perovskite coating increase the interfacial contact resistance, thereby affecting the output performance and service life of the solid oxide fuel cell.
分别对单电池 63、 单电池 66、 燃料电池堆单元 68和燃料电池堆单元 69 进行阻抗测试， 单电池 63与燃料电池堆单元 68的阻抗之差即为金属连接件 61的阻抗， 单电池 66与燃料电池堆单元 69的阻抗之差即为金属连接件 64的 阻抗， 结果参见图 10和图 11 , 图 10为本发明比较例 2提供的单电池 63和燃 料电池堆单元 68的阻抗曲线， 其中曲线 91为单电池 63的阻抗曲线， 曲线 92 为燃料电池单元 68的阻抗曲线； 图 11为本发明比较例 2提供的单电池 66和 燃料电池堆单元 69的阻抗曲线， 其中， 曲线 101为单电池 66的阻抗曲线， 曲 线 102为燃料电池单元 69的阻抗曲线。 The single cell 63, the single cell 66, the fuel cell stack unit 68, and the fuel cell stack unit 69 are respectively subjected to impedance test, and the difference between the impedance of the single cell 63 and the fuel cell stack unit 68 is the impedance of the metal connecting member 61, and the single cell 66 The difference from the impedance of the fuel cell stack unit 69 is the impedance of the metal connector 64. The results are shown in Figs. 10 and 11, which are impedance curves of the unit cell 63 and the fuel cell stack unit 68 provided in Comparative Example 2 of the present invention. The curve 91 is the impedance curve of the unit cell 63, and the curve 92 is the impedance curve of the fuel cell unit 68. FIG. 11 is the impedance curve of the unit cell 66 and the fuel cell stack unit 69 provided by the comparative example 2 of the present invention, wherein the curve 101 is The impedance curve of the single cell 66, Line 102 is the impedance curve of fuel cell unit 69.
由图 10和图 11可知，采用常规的涂有单层钙钛矿涂层的金属连接件得到 的燃料电池反应堆的欧姆电阻值与单电池本身的欧姆电阻值相差较大，说明常 规的涂有单层钙钛矿涂层的金属连接件的电阻较大，说明单层钙钛矿涂层增加 了金属连接件的电阻。  It can be seen from FIG. 10 and FIG. 11 that the ohmic resistance value of the fuel cell reactor obtained by using the conventional metallized joint coated with the single-layer perovskite coating differs greatly from the ohmic resistance value of the single-cell itself, indicating that the conventional coating is coated. The single-layer perovskite coated metal joint has a higher electrical resistance, indicating that the single-layer perovskite coating increases the electrical resistance of the metal joint.
由上述实施例及比较例可知， 本发明提供的具有金属连接件基底 /合金粉 体涂层 /4弓钛矿涂层结构的金属连接件中， 钙钛矿涂层、 合金粉体涂层和金属 连接件基底之间的界面结合较为紧密，用于固体氧化物燃料电池堆时不会增加 界面电阻， 从而能够提高固体氧化物燃料电池堆的输出性能和使用寿命。  It can be seen from the above embodiments and comparative examples that the present invention provides a metal connector having a metal connector base/alloy powder coating/4 perovskite coating structure, a perovskite coating, an alloy powder coating, and The interface between the metal connector substrates is tightly combined, and the interface resistance is not increased when used in a solid oxide fuel cell stack, thereby improving the output performance and service life of the solid oxide fuel cell stack.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本 发明。 对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见 的， 本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下， 在 其它实施例中实现。 因此， 本发明将不会被限制于本文所示的这些实施例， 而 是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。  The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded to the broadest scope of the principles and novel features disclosed herein.

Claims

权 利 要 求 Rights request
1、 一种耐高温金属连接件， 包括： 1. A high temperature resistant metal connector, comprising:
金属连接件基底；  Metal connector base;
复合在所述金属连接件基底表面的合金粉体涂层；  An alloy powder coating compounded on a surface of the metal connector substrate;
复合在所述合金粉体涂层表面的钙钛矿涂层。  A perovskite coating compounded on the surface of the alloy powder coating.
2、 根据权利要求 1所述的金属连接件， 其特征在于， 所述合金粉体涂层 中的合金粉体为 Cr基合金粉体。  The metal connecting member according to claim 1, wherein the alloy powder in the alloy powder coating layer is a Cr-based alloy powder.
3、根据权利要求 2所述的金属连接件， 其特征在于， 所述 Cr基合金粉体 为 Fe-Cr合金粉体或 Ni-Cr合金粉体。  The metal connecting member according to claim 2, wherein the Cr-based alloy powder is a Fe-Cr alloy powder or a Ni-Cr alloy powder.
4、 根据权利要求 1~3任意一项所述的金属连接件， 其特征在于， 所述合 金粉体涂层中的合金粉体的粒度为 0.01mm~0.15mm。  The metal connector according to any one of claims 1 to 3, wherein the alloy powder in the alloy powder coating has a particle size of 0.01 mm to 0.15 mm.
5、 根据权利要求 1~3任意一项所述的金属连接件， 其特征在于， 所述合 金粉体涂层的厚度为 0.02mm~0.2mm。  The metal connector according to any one of claims 1 to 3, wherein the alloy powder coating has a thickness of 0.02 mm to 0.2 mm.
6、 根据权利要求 1所述的金属连接件， 其特征在于， 所述钙钛矿涂层中 的钙钛矿为锶掺杂的锰酸镧、 锶掺杂的钴酸镧或锶和铁掺杂的钴酸镧。  6. The metal connector according to claim 1, wherein the perovskite in the perovskite coating is cerium-doped lanthanum manganate, cerium-doped lanthanum cobaltate or lanthanum and iron. Miscellaneous cobalt lanthanum.
7、 根据权利要求 1所述的金属连接件， 其特征在于， 所述钙钛矿涂层中 钙钛矿的粒度为 0.01mm~0.15mm。  The metal connector according to claim 1, wherein the perovskite has a particle size of from 0.01 mm to 0.15 mm.
8、 根据权利要求 1、 6或 7所述的金属连接件， 其特征在于， 所述 4弓钛矿 涂层的厚度为 0.02mm~0.15mm。  The metal connector according to claim 1, 6 or 7, wherein the thickness of the 4 canadite coating is 0.02 mm to 0.15 mm.
9、 权利要求 1所述的耐高温金属连接件的制备方法， 包括以下步骤： 采用等离子喷涂的方法向金属连接件基底表面喷涂合金粉体，在所述金属 连接件基底上形成合金粉体层； 金粉体层上形成钙钛矿涂层。  9. The method for preparing a high temperature resistant metal connector according to claim 1, comprising the steps of: spraying a metal powder onto the surface of the metal connector substrate by plasma spraying, and forming an alloy powder layer on the metal connector substrate. A perovskite coating is formed on the gold powder layer.
10、 一种固体氧化物燃料电池堆， 包括： 堆叠结构和容纳所述堆叠结构的 壳体， 其中， 所述堆叠结构包括：  10. A solid oxide fuel cell stack, comprising: a stacked structure and a housing accommodating the stacked structure, wherein the stacked structure comprises:
两个以上固体氧化物燃料电池，所述固体氧化物燃料电池包括依次堆叠的 集流层、 阴极、 电解质层和阳极； 相邻两个固体氧化物燃料电池通过权利要求 1~9任意一项所述的耐高温 金属连接件相堆叠。 More than two solid oxide fuel cells comprising a current collector layer, a cathode, an electrolyte layer and an anode stacked in sequence; Two adjacent solid oxide fuel cells are stacked by the high temperature resistant metal connector of any one of claims 1 to 9.
PCT/CN2011/074141 2011-05-17 2011-05-17 Heat-resistant metal connecting component, method producing the same and solid oxide fuel cell stack WO2012155333A1 (en)

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WO2006059942A1 (en) * 2004-11-30 2006-06-08 Sandvik Intellectual Property Ab Strip product forming a surface coating of perovskite or spinel for electrical contacts
EP1850412A1 (en) * 2006-04-26 2007-10-31 Technical University of Denmark A multi-layer coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1217878C (en) * 1998-07-24 2005-09-07 苏舍赫克希斯公司 Calcium-titanium ore used as coating of switching device
WO2006059942A1 (en) * 2004-11-30 2006-06-08 Sandvik Intellectual Property Ab Strip product forming a surface coating of perovskite or spinel for electrical contacts
EP1850412A1 (en) * 2006-04-26 2007-10-31 Technical University of Denmark A multi-layer coating

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