CA1267931A - Stabilized carbonate fuel cell cathode - Google Patents

Stabilized carbonate fuel cell cathode

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Publication number
CA1267931A
CA1267931A CA000504276A CA504276A CA1267931A CA 1267931 A CA1267931 A CA 1267931A CA 000504276 A CA000504276 A CA 000504276A CA 504276 A CA504276 A CA 504276A CA 1267931 A CA1267931 A CA 1267931A
Authority
CA
Canada
Prior art keywords
cathode
layer
accordance
constituent
composite structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CA000504276A
Other languages
French (fr)
Inventor
Prabhakar Singh
Randolph Muchmore Bernard
Lawrence Michael Paetsch
Ronald Dean Chamberlin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuelcell Energy Inc
Original Assignee
Energy Research Corp
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 Energy Research Corp filed Critical Energy Research Corp
Priority to CA000504276A priority Critical patent/CA1267931A/en
Application granted granted Critical
Publication of CA1267931A publication Critical patent/CA1267931A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9016Oxides, hydroxides or oxygenated metallic salts
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/14Fuel cells with fused electrolytes
    • H01M8/141Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/14Fuel cells with fused electrolytes
    • H01M2008/147Fuel cells with molten carbonates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0048Molten electrolytes used at high temperature
    • H01M2300/0051Carbonates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/14Fuel cells with fused electrolytes
    • H01M8/148Measures, other than selecting a specific electrode material, to reduce electrode dissolution
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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

Abstract

ABSTRACT OF THE DISCLOSURE
Migration and/or dissolution of Ni from the cathode of a molten carbonate fuel cell is retarded by the incorporation of a constituent adapted to effect such retardation.

Description

~26~9t3~ ~

Backqround of the Inventlon This invention relates to stable cathodes and, in particular, to a mechani~m for reta~ding nickel oxide 10QS
in the cathode of a molten carbonate fuel ,cell.
Cathode~ for use in molten carbonate euel cell generally employ lithiated nickel oxide as the catbode constituent. vuring long term operation o;~ the fuel cell i~ is found that dissolution of nickel oxide and precipation of the nickel occur~. As a result, the cathode is consumed at the cathode-electrolyte irlterface, thereby greatly decreasing the cathode surface area.
Fur~hermore, nickel precipitates i~to the matrix increasing the likelihood that electrical shorting o~ the - cell may occur.
In d molten carbonate fuel cell the severity of the above effects has been found to be inr~uenced by the gas composition used, the matrix thickness, load conditions and other cell characteristics. ~owever, to date, elimination of these effect~ has not been pos~ible under normal cell operating conditions. Al~o, while attempts have been made to develop alternative cathode materials, ~atisfactory su~stitute materials have not a~ yet been found.
It is therefore a primary object of the present invention to provide a mechanism for retarding nickel loss in a nickel oxide cathode.
It is a further object of the present invention to provide a mechani m for retarding nickel di~solution and nickel precipitation in a nickel oxide cathode electrode.

3~ In accordance with the principles o~ the present invention, the above and other objectives are realized by providing in the cathode and electrolyte assembly of a molten carbonate fuel cell a constituent adapted to retard nic~el dissolution and/or migration from th~ cathode -31 -- ;

Preferably, the re~arding constituent comprises multivalent tran~ition or alkaline earth m~tals and, more preferably, oxides of metals selectsd from the group consisting o~ i~on, manganeseS cobalt, ba~ium and strontium.
It is also preferable, where the cathode material is lithiated nickel oxide, for the constituent oxides to also be lithiated. A preferable lithiated reta~ding constituent is a mixture of lithium iron oxides. A
10 preferable mixture of such oxides is a mix'cure of LiFeO2 and LiFesO~.
In practice of ths invention, the constituent ean be incorporated into or formed as a di~crete layer and the layer then situated between the cathode and electrolyte, 15 Alternatively, the con~tituent may be incorporated into the cathode and/or the electrolyte as a diæpersion Additionally, it may be incorporated into the electrolyte as a homogeneous saturated solution.
Description of the Drawings $he above and other features and aspects o~ the pre~ent invention will become more apparent upon reading ~he following detailed description in con junction with the acco~panying drawings in which:
FIG. 1 shows a molten carbonate fuel cell employing a stabilizing mechanism in accordance with the principles of the present invention;
~ IG. 2 shows scanning electron miscroscope photographs of the cross section of an anode-electrolyte-cathode section of a fuel cell of the type shown in YIG. l;
~ IG~ 3 illustrates energy dispersive spectroscopy photographs of various areas of the ~ection of FIG. 2;
FIG. 4 set~ forth a comparison of the electrolyte of a cell having the stabilizin~ mechanism of the invention and a standard cell; and 12G793~

3.
FIG. 5 illustrates the performance characteristics o~
th~ cells of FIG. 4.
Detaileq Description In ~IG. 1, a molten carbonate fuel ce:Ll 1 include~
inlet manifold~ or hou~ing~ 2 and 3 for coupling fuel procesQ gas and oxidant process gas to anode and cathode electrode~ 4 and 5, respectively. The anQde 4 of the cell 1 ~ypically comprises a porous nickel material. ~he electrolyte matrix or tile 6, on the other hand, typically comprises an alkali carbonate material and a binder which for present purposes are assumed to be lithium and potassium carbonate and lithium aluminate, respectively.
Similarly, for present purposes, the cathode 5 is assumed to comprise lithiated nickel oxide of the general formulation ~iX~ XO.
In accordance with the principles of the present invention, the cell 1 i8 further adapted so as to inhibit or retard nickel dissolution and/or migration from the cathode 5. In the pre-~ent illustrative case, the latter is accomplished by providing a discrete layer 7 at the cathode-electrolyte interface. The layer 7, in turn, includes a constituent for providing the aforementioned retardation.
In accordance with the invention, a pre~erabl~
25, constituent for the retarding layer 7 includes one or more COmpOUlld8 of tran~ition or alkaline earth metals and, more preferably, one or more mixed oxides of metals ~elected ~xom the group consisting of iron, manganese, cobalt, barium and strontium. It is further prefera~le,where the 3~ cathode is litbiated, as in the pre~ent illustrative case, for the mixed oxides to also be lithiated. An oxide which has been found usable is lithiated iron oxide having the formulation LiPexoy and a particular preferred mixtu~e is LiFeO2 and ~i~e5V8~

~J
~1;~93~

A number of molten carbonate ~uel cells employing a layer 7 comprised of a mixtur~ of LiFeO2and Li~e 58 have been constructed and operated, In all these cells, the layer 7 is fabricated by mixing Pe203 and tLiR) 2CO3 5 powder~ in a heated atmosphere containing air and carbon dioxide. A typical temperature for the atmosphere i~ 650 degrees centrigrade and a typical percentage of carbon dioxide in air is 5-10 percent.
Heating of the mixed compounds in this atmo phere converts the compounds to a mixt~re of lithiated iron oxides having the forln~lation LiFeO2 and LiF~sO~. This mixture is then washed, filtered, dried and ground to produce submicron size particles. The resultant particles are then tape ca~t to produce a continuous laye~ or tape of 75 to 150 micrometer~ thickne-~s and pore ~ize o~ 0.3 to 0.4 micrometers.
Cells are constructed using a standard anode, a standa~d electrolyte matrix or tile, ~tanda~d anode and cathode current collectors and a standard composit~
20 lithiated ~iO cathode. In constructing a cell the mix~d iron oxide tape is ~ituated at the interface between the cathode and the tile in accordance with ~I~. 1.
Cells made in accordance with the above poCedure were opera~ed for lU~ hour~ and post examination of the 25 electrolyte tile~ of the cells showed no evidence of nickel metal precipitate either near the cathode/tile interface or near the anode/tile interface~ Fur~hermore, f cell re~istance and cell voltage were ~ound substantially unaltered by the presence of the layee. Also, retardation 30 of the dissolution of ~iO feom the cathode was confirmed by independent out-o~-cell solubility meas~rements which showed a ~ive fold decrease in ~olubility of NiO.
FIG. 2 shows a scannin~ electron microscope pho~ograph oE ~ile 6, retarding layer 7 and cathode 5 oE

~26i~3~ ~

cell 2-008 constructed as above described. FIG. 3 illustrates the accompanying ene~gy disper~ive spectroscopy ~can~ ~or variou~ regions of thi~ sandwich.
As can be ~een rom FIG. 3, ~o nickel or iron i~ present in the ~egion A co~responding to the central a~ea Oe tbe tile 6 Likewise, nickel and iron are a~sent from the region ~ which is the tile 51de o~ the tll~-retarding layer interface. Similarly, the region C at the retarding layer Yide of this interface al~o shows no Ni. The region D of the layer close t4 the cathode also evidences an absence of ~i. Finally, the region ~ which represents a thin ~ilm of material which adheres to the retarding layer rom the cathode, ~hows the expected Ni alo~g with some trace of iron.
The above results aptly demonstrate the barrier or retarding action of the mixed errite layer 7 toward the migration of Ni. Sub3equent chemical analysi~ of tbe ~andwiched layers by atomic a~sorptio~ found 0.~
micrograms Ni/hr/sq. cm., compared to the usual amount~ in 20 cells without the layer 7 of up to 12.
FIG. 5 ~how the performance characteri~tics of a cell 7-62 employing a layer in accord witb the invention and a conventional cell 7-52 having similar component characteri tic~, but without the layer 7. FI~. 4 shows optical photographs of the cross-Qections of tiles 6 of each of the cells 7-62 and 7-52.
As can be seen from FIG. 5, no performance dilution is evidenced by use of the layer 7. A}so, FIG. 4 demonstrate~ that while Ni particles are present in each of the tiles of the cell~ 7-62 and 7 52, those ~f the tile 7-62 employing the layer 7 are of much smaller size and number. Analysis of the~e tiles by atomic absorption found only 0.9 micrograms Ni/hr~8~.cm. in the tile of cell 7-62, with 5.81 in the tile of cell 7-52. Again, ~IL~93~

therefore, as in the previous example, the 8uperior Ni retardation capa~ilit~ o~ the present cells i~ apparent.
I~ should be noted ~hat while the retarding con~tituant has been deQcribed and showsl as forming a discrete layer, it i~ within the contemplation of the invention that the constituent a~so be incorporated into the cathode and/or the electrolyte tile. ~hus, an additive comprised of the material discussed above for the layer 7 can be directly incorporated into the cathode or the electrolyte tile as a separate phase (dispersion).
Additionally, the con~tituent may be incor~orated ints ~he electrolyte as a homogeneous, saturated solution.
In all cases, it is understood tha~ the above-identified arrangement~ are merely illustrative of the many possible specific embodiment~ which represent applications of the present invention. Numerous and varied other arrangements can readily be devised in accordance with the principles of the present invention without departing from the spirit and scope o~ the 1 20 invention.
, ;~5

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composite structure for use in a molten carbonate fuel cell comprising:
an anode layer;
a cathode layer comprising a nickel oxide material;
an electrolyte layer situated between said anode and cathode layers;
and a constituent for retarding migration and/or dissolution of said nickel-oxide constituent from said cathode, said retarding constituent comprising one or more oxides of alkaline earth metals.
2. A composite structure in accordance with claim 1 wherein:
said constituent is in layer situated at the interface of said cathode and electrolyte layers.
3. A composite structure in accordance with claim 1 wherein:
said layer is a discrete layer.
4. A composite structure in accordance with claim 1 wherein:
said constituent is incorporated as a separate phase into one of said electrolyte layer and said cathode layer.
5. A composite structure in accordance with claim 4 wherein:
said constituent is added to said cathode layer.
6. A composite structure in accordance with claim 1 wherein:
said constituent is incorporated into said electrolyte layer as a homogeneous, saturated solution.
7. A composite structure in accordance with claim 1 wherein:
said metals are selected from the group consisting of barium and strontium.
8. A composite structure in accordance with claim 7 wherein:

said oxides are lithiated.
9. A composite structure in accordance with claim 8 wherein:
said cathode comprises lithiated nickel oxide of the formula LixNil-xO.
CA000504276A 1985-04-19 1986-03-17 Stabilized carbonate fuel cell cathode Expired - Lifetime CA1267931A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA000504276A CA1267931A (en) 1985-04-19 1986-03-17 Stabilized carbonate fuel cell cathode

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US06/725,257 US4992342A (en) 1985-04-19 1985-04-19 Stabilized carbonate fuel cell cathode
US725,257 1985-04-19
CA000504276A CA1267931A (en) 1985-04-19 1986-03-17 Stabilized carbonate fuel cell cathode

Publications (1)

Publication Number Publication Date
CA1267931A true CA1267931A (en) 1990-04-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
CA000504276A Expired - Lifetime CA1267931A (en) 1985-04-19 1986-03-17 Stabilized carbonate fuel cell cathode

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US (1) US4992342A (en)
JP (1) JPH06101337B2 (en)
CA (1) CA1267931A (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
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US4663250A (en) * 1986-03-12 1987-05-05 Institute Of Gas Technology Reduction of electrode dissolution
JP2813350B2 (en) * 1988-07-05 1998-10-22 三菱電機株式会社 Molten carbonate fuel cell
JP2708820B2 (en) * 1988-11-10 1998-02-04 三洋電機株式会社 Electrolyte of molten carbonate fuel cell
JPH0455086A (en) * 1990-06-22 1992-02-21 Meidensha Corp Production of brazing material
US5340665A (en) * 1992-09-03 1994-08-23 Ceramatec, Inc. Creep resistant, metal-coated LiFeO2 anodes for molten carbonated fuel cells
DE4235514C2 (en) * 1992-10-21 1995-12-07 Fraunhofer Ges Forschung Porous oxygen-consuming electrode, process for its production and its use
DE4241266C1 (en) * 1992-12-08 1994-07-21 Mtu Friedrichshafen Gmbh Cathode prodn. for carbonate melt fuel cell
CN1059757C (en) * 1993-07-10 2000-12-20 北京大学 Secondary battery with lithium ion aqueous solution
US5589287A (en) * 1993-10-18 1996-12-31 Matsushita Electric Industrial Co., Ltd. Molten carbonate fuel cell
DE4440696C2 (en) * 1994-11-15 1997-07-17 Mtu Friedrichshafen Gmbh Process for producing a double-layer cathode for molten carbonate fuel cells and the double-layer cathode produced by the process
KR100224546B1 (en) * 1996-08-31 1999-10-15 박호군 Cathode for molten carbonate fuel cell to which alkali earth metal oxide is added and a process for preparing thereof
US5851689A (en) * 1997-01-23 1998-12-22 Bechtel Corporation Method for operating a fuel cell assembly
US6017654A (en) * 1997-08-04 2000-01-25 Carnegie Mellon University Cathode materials for lithium-ion secondary cells
US6878490B2 (en) * 2001-08-20 2005-04-12 Fmc Corporation Positive electrode active materials for secondary batteries and methods of preparing same
KR100874331B1 (en) * 2006-12-28 2008-12-18 두산중공업 주식회사 Method for manufacturing electrolyte-impregnated cathode in molten carbonate fuel cell
US7943269B2 (en) * 2008-02-26 2011-05-17 University Of Rochester Ion-/proton-conducting apparatus and method
DE102022000153A1 (en) * 2022-01-17 2023-07-20 KS iPR UG (haftungsbeschränkt) ELECTROLYTE MEMBRANE FOR THE SEPARATION OF WATER VAPOR INTO HYDROGEN AND OXYGEN USING ELECTRIC ENERGY AND/OR GENERATION OF ELECTRICAL ENERGY USING HYDROGEN AND OXYGEN BY A LITHIATED IRON OXIDE - IRON REDOX REACTION IN A LIQUID CARBONATE SALT

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US3505120A (en) * 1966-11-23 1970-04-07 Texas Instruments Inc Fuel cell comprising foraminous silver electrode having a porous layer of magnesium oxide
US4329403A (en) * 1981-04-27 1982-05-11 Energy Research Corporation Electrolyte-electrode assembly for fuel cells
US4411968A (en) * 1981-09-30 1983-10-25 United Technologies Corporation Molten carbonate fuel cell integral matrix tape and bubble barrier
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Also Published As

Publication number Publication date
US4992342A (en) 1991-02-12
JPS622458A (en) 1987-01-08
JPH06101337B2 (en) 1994-12-12

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