WO2011116794A1 - Réduction des tensions thermomécaniques dans un assemblage de piles à combustible à oxyde solide ou dans un assemblage de piles à électrolyse - Google Patents

Réduction des tensions thermomécaniques dans un assemblage de piles à combustible à oxyde solide ou dans un assemblage de piles à électrolyse Download PDF

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Publication number
WO2011116794A1
WO2011116794A1 PCT/EP2010/001938 EP2010001938W WO2011116794A1 WO 2011116794 A1 WO2011116794 A1 WO 2011116794A1 EP 2010001938 W EP2010001938 W EP 2010001938W WO 2011116794 A1 WO2011116794 A1 WO 2011116794A1
Authority
WO
WIPO (PCT)
Prior art keywords
stack
end plate
cell
solid oxide
cell stack
Prior art date
Application number
PCT/EP2010/001938
Other languages
English (en)
Other versions
WO2011116794A8 (fr
Inventor
Jørgen Gutzo LARSEN
Caspar Buchholt Frederiksen
Sune Demuth DANØ
Original Assignee
Topsoe Fuel Cell A/S
Frandsen, Henrik Lund
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 Topsoe Fuel Cell A/S, Frandsen, Henrik Lund filed Critical Topsoe Fuel Cell A/S
Priority to PCT/EP2010/001938 priority Critical patent/WO2011116794A1/fr
Publication of WO2011116794A1 publication Critical patent/WO2011116794A1/fr
Publication of WO2011116794A8 publication Critical patent/WO2011116794A8/fr

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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
    • H01M8/248—Means for compression of the fuel cell stacks
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/2432—Grouping of unit cells of planar configuration
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • 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
    • 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
    • H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
    • 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 relates to reduction of the thermo mechanical tensions in fuel cell stacks or electrolysis cell stacks, in particular high temperature fuel cell stacks or electrolysis cell stacks.
  • the end plate according to the invention can, however, also be used for other types of fuel cell stacks such as Polymer Electrolyte Fuel cell (PE ) stacks or Direct Methanol Fuel Cell (DMFC) stacks. Further, the invention can also be used for elec- trolysis cell stacks such as Solid Oxide Electrolysis Cell stacks .
  • PE Polymer Electrolyte Fuel cell
  • DMFC Direct Methanol Fuel Cell
  • a Solid Oxide Fuel Cell comprises a solid electrolyte that enables the conduction of oxygen ions, a cathode where oxygen is reduced to oxygen ions and an anode where hydrogen is oxidised.
  • the overall reaction in a SOFC is that hydrogen and oxygen electrochemically react to produce electricity, heat and water.
  • the anode normally possesses catalytic ac- tivity for the steam reforming of hydrocarbons, particularly natural gas, whereby hydrogen, carbon dioxide and carbon monoxide are generated.
  • Steam reforming of methane, the main component of natural gas can be described by the following equations:
  • an oxidant such as air is supplied to the solid oxide fuel cell in the cathode region.
  • Fuel such as hydrogen is supplied in the anode region of the fuel cell.
  • a hydrocarbon fuel such as methane is supplied in the anode region, where it is converted to hydrogen and carbon oxides by the above reactions.
  • Hydrogen passes through the porous anode and reacts at the anode/- electrolyte interface with oxygen ions generated on the cathode side that have diffused through the electrolyte. Oxygen ions are created in the cathode side with an input of electrons from the external electrical circuit of the cell.
  • interconnects serve as a gas barrier to separate the anode (fuel) and cathode (air/oxygen) sides of adjacent cell units, and at the same time they enable current conduction between the adjacent cells, i.e. between an anode of one cell with a surplus of electrons and a cathode of a neigh ⁇ bouring cell needing electrons for the reduction process.
  • interconnects are normally provided with a plural- ity of flow paths for the passage of reactant gasses: fuel gas on one side of the interconnect and oxidant gas on the opposite side.
  • a solid oxide fuel cell (SOFC) stack is thus a sandwich composed of ceramic fuel cells and steel interconnects and spacers. These different materials are "glued" together with glass seals to form a rigid structure. The use of such different materials makes it impossible to avoid some differences in thermal expansion coefficients (TEC) .
  • TEC thermal expansion coefficients
  • the stack can be subjected to high temperatures up to approximately 1000 degrees Celsius causing tempera- ture gradients in the stack and thus different thermal expansion of the different components of the stack.
  • the resulting thermal expansion may lead to a reduction in the electrical contact between the different layers in the stack.
  • the thermal expansion may also lead to cracks and leakage in the gas seals between the different layers leading to poorer functioning of the stack and a reduced power output.
  • the mismatch in TEC values results in thermomechanic stresses and crack inducing energy.
  • the potential energy which can be released when the endplate and the stack delaminates is approximately propor ⁇ tional to the thickness of the endplate and proportional to the square of the difference between the stack TEC and the endplate TEC.
  • both the match of TEC values and the thickness of the endplates are crucial for the integrity of the cell stack.
  • the crack inducing energy will result in de- lamination of the stack and loss of integrity unless the stack is protected by a compression system.
  • US 5009968 seeks to solve the problem of deformation of the thick endplates themselves, by positioning these outside the stack separated by an insulation material.
  • an electrically conducting flexible membrane integral with a box-like wall structure is positioned at each end of the stack .
  • US 5009968 seek to solve the problem of deformation of the thick endplates outside the insulation and thus external relative to the hot stack, still the problem of differences in thermal expansion coefficients (TEC) within the stack including the internal end plates remains unsolved.
  • TEC thermal expansion coefficients
  • an end plate to reduce the thermo mechanical tensions in a cell stack is provided for especially solid oxide fuel cell stacks or solid oxide electrolysis cell stacks, but also potentially to other known fuel cell types as already mentioned.
  • the cell stack will predominantly be regarded as a black box which generates electricity and heat when supplied with oxidation gas and fuel gas.
  • the function and internal components of the fuel cell stack is considered known art and is not the subject of this invention.
  • the thick end plate for known art cell stacks has two func ⁇ tions; A: to close the stack, and B: to distribute load from the compression system.
  • this functionality is divided onto two end plates; a thin end plate for A (e.g. 0.3 mm vs. 8 mm in a known stack) and a thick external compression plate for B.
  • the thin end plate reduces the crack inducing energy by more than a factor of 50 and improves the stack integrity significantly.
  • it is essential that the thick compression plate which distributes the compression force can expand and contract independently of the stack.
  • the thin endplates are in one embodiment made in a corresponding thickness as the interconnect plates.
  • End plate for reduction of the thermo mechanical tensions in a cell stack, at least one of said end plate is arranged in connection to at least one end of the cell stack, said stack further comprising at least one cell, the at least one cell comprising an anode, a cathode and an electrolyte, said at least one cell is either a Solid Oxide Fuel Cell or a Solid Oxide Electrolysis Cell, wherein said end plate is planar, the material of said end plate has a thermal expansion coefficient corresponding the thermal ex ⁇ pansion coefficient of the material of said cell, prefera ⁇ bly within the range 9*10 "6 K "1 to 14*10 ⁇ 6 K "1 and the thick ⁇ ness of said end plate is within the range 0.001 mm to 1 mm, preferably within the range 0.05 mm to 0.3 mm.
  • said stack further comprises at least one pressure plate to distribute a compression force to said stack, said at least one pres- sure plates is arranged on the opposite side of said at least one end plate relative to the cells.
  • End plate according to feature 2 wherein said stack further comprises at least one insulation member located between said at least one end plate and said at least one corresponding pressure plate. 4. End plate according to any of the preceding features, wherein said at least one end plate is made of a metal with high chrome content . 5. End plate according to any of the preceding features, wherein said at least one end plate has side lengths corre- sponding the side lengths of said at least one cell in said cell stack. 6. End plate according to any of the preceding features, said cell stack comprises at least two cells and further comprises at least one Inter Connect plate interposed between said cells, wherein said at least one end plate has a thickness corresponding the thickness of said Inter Connect plate.
  • a Solid Oxide Fuel Cell Stack or a Solid Oxide Elec ⁇ trolysis Stack comprising at least one end plate according to any of the features 1 to 6.
  • Fig. 1 shows a. side view of a fuel cell stack or an electrolysis cell stack according to one embodiment of the in ⁇ vention including a thin top end plate and a thin bottom end plate.
  • Fig. 2 shows a side view of a fuel cell stack or an electrolysis cell stack according to one embodiment of the invention including thin endplates, insulation and thick com ⁇ pression plates.
  • Fig. 3 shows a side view of a conventional fuel cell stack with thick end plates and transportation rods. Position number overview:
  • Thick end plate part of stack (top) Thick end plate part of stack (top) .
  • FIG. 1 One embodiment of the invention is shown on figure 1.
  • the embodiment shows a fuel cell stack or an electrolysis cell stack (100) with thin internal endplates provided at the top (101) and the bottom (102) of the stack.
  • the stack is an assembly of alternating layers of fuel cells or elec ⁇ trolysis cells (103) and metal interconnects (104).
  • the risk of delamination between the stack and the end plates is reduced by using end plate material and thickness corre- sponding to the material and thickness of the interconnects .
  • the stack according to the embodiment shown in figure 1 can preserve its integrity at room temperature as it is shown on the figure, i.e. with no need for further external compression forces applied to ensure that thermomechanic stresses and crack inducing energy occurs.
  • the simple stack with reduced components as compared to known art cell stacks is a robust unit which can be handled, transported and installed at room temperatures without the risk of de- lamination as it is pictured on figure 1, no protecting compression system is necessary.
  • a further embodiment of the invention is shown on figure 2.
  • This embodiment shows a fuel cell stack or an electrolysis cell stack (200) with thin internal endplates provided at the top (201) and bottom (202) corresponding the cell stack according to figure 1.
  • the cell stack comprises alternating layers of fuel cells or electrolysis cells (203) and inter ⁇ connects (204).
  • figure 1 shows a cell stack in a situation at room temperature and in a mode where the stack can be handled however
  • figure 2 shows a cell stack accord ⁇ ing to the invention in a situation which can be the opera- tion mode.
  • an external compression force (F) though reduced according to the invention, can be needed.
  • the integrity of the cell stack is maintained even though the external compres ⁇ sion force is applied via thick rigid compression plates. This is achieved by separation the thin internal end plates (201 and 202) from the thick external rigid compression plates (205 and 206) . The separation is both mechanical, electrical and thermal.
  • the separation is achieved by an intermediate thermal and electrical insulation layer (207) positioned between the top end plate and the top compression plate and a gasket and thermal and electrical insulation layer (208) positioned between the bottom end plate and the bottom compression plate.
  • This decoupling of the thick compression plates from the stack unit including the thin endplates allows for relative free movement between the stack unit and the compression plates as compared to the known art thick endplates which are integral with, and fixed to the stack.
  • the integrity of the cell stack is ensured, and as the TEC of the stack components including the thin end plates are matched by corresponding thicknesses and materials, the thermomechanic stresses and crack inducing energy in the stack unit also in the operation mode according to figure 2 is reduced.
  • FIG 3 a prior art fuel cell stack or electrolysis cell stack (300) is shown.
  • the stack comprises alternating layers of fuel cells or electrolysis cells (303) and interconnects (304) .
  • Endplates are positioned at the top (305) and at the bottom (306) of the stack. These endplates serve to close the stack as well as to distribute load from the compression system and even though they are integral with the thin layers of the stack they thus have to be thick and rigid.
  • this prior art fuel cell stack has to be subjected to a compression force.
  • the compression force is provided by transporting rods (309) and compression springs (310) for stack compression at room temperature.
  • the stack will de- laminate due to the internal thermomechanic stresses and crack inducing energy caused by the mismatch in TEC values of the stack components: the cells, the thin interconnects and the thick rigid endplates .

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

Abstract

La configuration d'une double plaque d'extrémité (101, 102) comprenant une plaque d'extrémité interne fine destinée à un assemblage de piles à combustible ou à un assemblage de piles à électrolyse (100) réduit les tensions thermomécaniques internes de l'assemblage. Ledit assemblage acquiert donc une intégrité qui rend moins utile, ou complètement inutile, une force de compression externe de l'assemblage à température ambiante, et qui rend également moins utile la force de compression de l'assemblage nécessaire lors du fonctionnement.
PCT/EP2010/001938 2010-03-26 2010-03-26 Réduction des tensions thermomécaniques dans un assemblage de piles à combustible à oxyde solide ou dans un assemblage de piles à électrolyse WO2011116794A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2010/001938 WO2011116794A1 (fr) 2010-03-26 2010-03-26 Réduction des tensions thermomécaniques dans un assemblage de piles à combustible à oxyde solide ou dans un assemblage de piles à électrolyse

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2010/001938 WO2011116794A1 (fr) 2010-03-26 2010-03-26 Réduction des tensions thermomécaniques dans un assemblage de piles à combustible à oxyde solide ou dans un assemblage de piles à électrolyse

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Publication Number Publication Date
WO2011116794A1 true WO2011116794A1 (fr) 2011-09-29
WO2011116794A8 WO2011116794A8 (fr) 2012-03-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140212783A1 (en) * 2011-09-07 2014-07-31 Topsøe Fuel Cell A/S Fuel cell stack with thin endplate with integrated gas distribution tubes

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0338823A1 (fr) * 1988-04-21 1989-10-25 Toa Nenryo Kogyo Kabushiki Kaisha Piles à combustible du type à électrolyte solide
US5009968A (en) 1989-09-08 1991-04-23 International Fuel Cells Corporation Fuel cell end plate structure
US20040101733A1 (en) * 2002-11-27 2004-05-27 Jean Yamanis Interconnect for solid oxide fuel cells
WO2005029618A2 (fr) * 2003-09-17 2005-03-31 Tiax Llc Dispositifs electrochimiques et composants de ceux-ci
JP2007273429A (ja) * 2006-03-31 2007-10-18 Dainippon Printing Co Ltd 固体酸化物形燃料電池、及びその製造方法
EP1879251A1 (fr) * 2006-07-14 2008-01-16 Topsøe Fuel Cell A/S Ensemble de compression, bloc de pile à combustible d'oxyde solide, procédé pour la compression du bloc de pile à combustible d'oxyde solide et son utilisation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0338823A1 (fr) * 1988-04-21 1989-10-25 Toa Nenryo Kogyo Kabushiki Kaisha Piles à combustible du type à électrolyte solide
US5009968A (en) 1989-09-08 1991-04-23 International Fuel Cells Corporation Fuel cell end plate structure
US20040101733A1 (en) * 2002-11-27 2004-05-27 Jean Yamanis Interconnect for solid oxide fuel cells
WO2005029618A2 (fr) * 2003-09-17 2005-03-31 Tiax Llc Dispositifs electrochimiques et composants de ceux-ci
JP2007273429A (ja) * 2006-03-31 2007-10-18 Dainippon Printing Co Ltd 固体酸化物形燃料電池、及びその製造方法
EP1879251A1 (fr) * 2006-07-14 2008-01-16 Topsøe Fuel Cell A/S Ensemble de compression, bloc de pile à combustible d'oxyde solide, procédé pour la compression du bloc de pile à combustible d'oxyde solide et son utilisation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140212783A1 (en) * 2011-09-07 2014-07-31 Topsøe Fuel Cell A/S Fuel cell stack with thin endplate with integrated gas distribution tubes
US10693152B2 (en) * 2011-09-07 2020-06-23 Haldor Topsoe A/S Fuel cell stack with thin endplate with integrated gas distribution tubes

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Publication number Publication date
WO2011116794A8 (fr) 2012-03-15

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