EP1711977A1 - Pile a combustible oxyde solide - Google Patents

Pile a combustible oxyde solide

Info

Publication number
EP1711977A1
EP1711977A1 EP03808290A EP03808290A EP1711977A1 EP 1711977 A1 EP1711977 A1 EP 1711977A1 EP 03808290 A EP03808290 A EP 03808290A EP 03808290 A EP03808290 A EP 03808290A EP 1711977 A1 EP1711977 A1 EP 1711977A1
Authority
EP
European Patent Office
Prior art keywords
fuel cell
solid oxide
oxide fuel
cermet
anode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03808290A
Other languages
German (de)
English (en)
Inventor
Boris L. Kuzin
Sergey M. Beresnev
Nina M. Bogdanovich
Edhem Kh. Kurumchin
Ana Berta Lopes Correia Tavares
Antonio Pirelli Labs ZAOPO
Yuri A. Pirelli Labs DUBITSKY
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.)
Pirelli and C SpA
Original Assignee
Pirelli and C SpA
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
Priority claimed from PCT/EP2003/014999 external-priority patent/WO2005064717A1/fr
Application filed by Pirelli and C SpA filed Critical Pirelli and C SpA
Priority to EP03808290A priority Critical patent/EP1711977A1/fr
Publication of EP1711977A1 publication Critical patent/EP1711977A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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 present invention relates to a solid oxide fuel cell, to a process for the preparation thereof, and to a method for producing energy by means of said solid oxide fuel cell.
  • SOFCs solid oxide fuel cells
  • Ni (nickel) cermets prepared by high temperature calcination of NiO and yttria-stabilized zirconia (YSZ) powders.
  • That paper describes the preparation of Cu-cermet anodes by adding Cu after preparing a porous layer of YSZ on a dense YSZ electrolyte layer.
  • Cu is added by aqueous impregnation with a concentrated solution of Cu(NO 3 ) 2 , followed by calcination to decompose the nitrate and form the oxide. Reduction of the oxides by H 2 at 800°C leads to the formation of metallic Cu.
  • YSZ is a cast dual tape with porosity introduced into one of the layers using graphite particles as pore formers. The cell with Cu-YSZ anode exhibits poor performance at 700°C.
  • E. Ramirez-Cabrera et al., Fifth European SOFC Forum, Proceedings vol. 1, edited by Joep Huijmans, page 531, 2002 relates to the preparation of Cu-CGO cermets (50 and 65 wt% Cu) from mixtures of CGO (Gd 0 ⁇ -Ce 09 Oj 95 )and either CuO or Cu 2 O powders.
  • the anode is produced by applying a slurry onto the surface of a dense CGO electrolyte pellet, and then sintering in air at 800°C or 1000°C. The pellets is then reduced in hydrogen atmosphere.
  • the paper is silent about characterization data of the anode struc- ture, but electronic conductivity in hydrogen atmosphere is measured to be of about 3000 S/cm at 700°C.
  • the electrical properties of composite materials depend mainly on microstructural properties, such as porosity, distribution of the metal phase, size of the grains and degree of contact between metal grains (J. Macek and M. Manrisek, Fizika A 4, 1995, 2, 413-422).
  • Fine particle size and pore size are known to improve the extension of the reactive sites, thus the performance, however could lead to transportation limitations for the fuel supply.
  • an increase of the metal content provide a better electronic conductivity, but metal having melting point lower than the sintering temperature (1200°C-13OO°C) tend to agglomerate and provide heterogeneous structures when present in the cermet in wt% similar or higher than that of the ceramic portion.
  • the Applicant has faced the problem of providing a SOFC having good electric (electronic plus ionic) conductivity at low temperature, e.g. 600°C-800°C, and long- lasting performances (structural and redox stability), desirable for any scale applications.
  • Applicant found that the problem could be solved by providing a SOFC with an anode comprising a cermet wherein the metallic and ceramic portions are uniformly interdispersed and provide a structure with a low surface area.
  • the metallic portion is present in a amount higher than 50 wt%, without yielding coarsening phenomena and thus assuring thermal and in-time stability of the percolating metal network.
  • the present invention relates to a solid oxide fuel cell including a cathode, an anode and at least one electrolyte membrane disposed between said anode and said cathode, wherein said anode comprises a cermet including a metallic portion and an electrolyte ceramic material portion, said portions being substantially uniformly interdispersed, said metallic portion having a melting point equal to or lower than 1200°C; said cermet having a metal content higher than 50 wt%, and a specific surface area equal to or lower than 5 m /g.
  • substantially uniformly interdispersed is meant that the portions of the cermet are intimately admixed in the entire volume of the cermet.
  • the metallic portion can be selected from a single metal such as copper, aluminum, gold, praseodymium, ytterbium, cerium, and alloys comprising one or more of these metals together.
  • the metallic portion is copper.
  • the metallic portion has a melting point higher than 500°C.
  • the metal content in a cermet suitable for the invention ranges between 60 wt% and 90 wt%.
  • the cermet suitable for the anode of the solid oxide fuel cell according to the invention has a specific surface area equal to or lower than 2 m /g.
  • the porosity of the cermet is equal to or higher than 40%.
  • the electrolyte ceramic material portion has a specific conductivity equal to or higher than 0.01 S/cm at 650°C.
  • it is doped ceria or La 1-x Sr x Ga ⁇ _ y MgyO 3 . ⁇ wherein x and y are comprised between 0 and 0.7 and ⁇ is from stoichiometry.
  • the ceria is doped with gadolinia (gadolinium oxide) or samaria (samarium oxide).
  • the ceramic material of the SOFC of the invention is yttria-stabilized zirconia (YSZ).
  • a first type of cathode for the solid oxide fuel cell of the invention comprises a metal such as platinum, silver or gold or mixtures thereof, and an oxide of a rare earth element, such as praseodymium oxide.
  • a second type of cathode comprises a ceramic selected from
  • Said second type of cathode can further comprise doped ceria.
  • a third type of cathode comprises a combination of the materials above mentioned for the cathodes of the first and second type.
  • the electrolyte membrane of the SOFC of the invention can be selected from the materials listed above in connection with the electrolyte ceramic material portion of the cermet.
  • the present invention relates to a method for producing energy comprising the steps of:
  • a) feeding at least one fuel into an anode side of a solid oxide fuel cell comprising an anode including a cermet comprising a metallic portion and an electrolyte ceramic material portion, said portions being substantially uniformly interdispersed, said metallic portion having a melting point equal to or lower than 1200°C; said cermet having a metal content higher than 50 wt%, and a specific surface area equal to or lower than 5 m /g; a cathode, and at least one electrolyte membrane disposed between said anode and said cathode;
  • a fuel suitable for the present invention can be selected from hydrogen; an alcohol such as methanol, ethanol, propanol; a hydrocarbon in gaseous form such as methane, ethane, butene; carbon dioxide, carbon monoxide, natural gas, reformed natural gas, biogas, syngas and mixture thereof, in the presence of water (steam fuel); or an hydrocarbon in liquid form, e.g. diesel, toluene, kerosene, jet fuels (JP-4, JP-5, JP-8, etc).
  • the fuel is hydrogen.
  • the solid oxide fuel cell of the invention operates at a temperature ranging between about 400°C and about 800°C, more preferably between about 500°C and about 7O0°C.
  • the solid oxide fuel cell can be prepared with methods known in the art. Advantageously it is prepared by the following process.
  • the present invention relates to a process for preparing a solid oxide fuel cell including a cathode, an anode and at least one electrolyte membrane disposed between said anode and said cathode, wherein said anode comprises a cermet including a metallic portion and an electrolyte ceramic material portion; said process comprising the steps of:
  • the step of providing the anode includes the steps of: a) providing a precursor of the metallic portion, said precursor having a particle size ranging between 0.2 ⁇ m and 5 ⁇ m; b) providing the electrolyte ceramic material having a particle size ranging between 1 ⁇ m and 10 ⁇ m; c) mixing said precursor and said ceramic material to provide a starting mixture; d) heating and grinding said starting mixture in the presence of at least one first dispersant; e) adding at least one binder and at least one second dispersant to the starting mixture from step d) to give a slurry; f) thermally treating the slurry to provide a pre-cermet; g) reducing the pre-cermet to provide the cermet.
  • particle size is intended the average particle size determined by physical separation methods, for example by sedimentography, as shown hereinbelow.
  • the slurry resulting from step e) is applied on the electrolyte membrane.
  • the precursor of the metallic portion is an oxide of the metals already listed above.
  • the oxide is Cu 2 O or CuO, the latter being preferred.
  • Preferably said precursor has a particle size ranging between 1 and 3 ⁇ m.
  • the ceramic material has a particle size ranging between 2 and 5 ⁇ m.
  • step d) is effected more than one time.
  • the first dispersant is a solvent or a solvent mixture.
  • it is selected from polar organic solvents, such as alcohols, polyols, esters, ketones, ethers, amides, optionally halogenated aromatic solvents such as benzene, chlorobenzene, dichlorobenzene, xylene and toluene, halogenated solvents such as chloroform and dichloroethane, or mixtures thereof. It ensures homogeneity to the starting mixture. Examples are provided in Table 1.
  • the second dispersant can be the same or different from the first dispersant.
  • the binder is soluble in the second dispersant.
  • it is selected from polymeric compounds containing polar groups such as polyvinylbutyral, nitrocellulose, polybutyl methacrylate, colophony, ethyl cellulose. Examples of mixtures binder/second dispersant are provided in Table 1.
  • Preferred binder is polyvinylbutyral.
  • Preferred first and second dispersants are ethanol and isopropanol.
  • step f) is carried out at a temperature ranging between about 700°C and about 1100°C, more preferably between about 900°C and about 1000°C.
  • the reduction step g) converts the metal oxide of the pre-cermet into metal.
  • this step is carried out at a temperature ranging between about 300°C and about 800°C, more preferably between about 400°C and about 600°C.
  • Hydrogen is a preferred reducing agent.
  • it is introduced in the reduction environment, for example an oven, which has been previously conditioned with an inert gas, such as argon.
  • hydrogen contains from 1 vol.% to 10 vol.% of water, preferably from 2 vol.% to 5 vol.%.
  • the present invention relates to a cermet including a metallic portion and an electrolyte ceramic material portion, said portions being substantially uniformly interdispersed, said metallic portion having a melting point equal to or lower than 1200°C; said cermet having a metal content higher than 50 wt%, and a specific surface area equal to or lower than 5 m /g.
  • FIG. 1 schematically illustrates a fuel cell power system
  • FIGS. 3a and 3b are micrographs of a Cu-SDC anode in (a) secondary electron emission and (b) backscattering modes;
  • Figures 1 schematically illustrate a solid oxide fuel cell power systems.
  • the solid oxide fuel cell (1) comprises an anode (2), a cathode (4) and an electrolyte membrane (3) disposed between them.
  • a fuel generally a hydrocarbon
  • Hydrogen is fed to the anode side of the solid oxide fuel cell (1).
  • Cathode (4) is fed with air.
  • the fuel cell (1) produces energy in form of heat and electric power.
  • the heat can be used in a bottoming cycle or conveyed to the fuel reformer (5).
  • the electric power is produced as direct current (DC) and may be exploited as such, for example in telecommunication systems, or converted into alternate current (AC) via a power conditioner (6).
  • DC direct current
  • AC alternate current
  • Cu 2 O powder (“analytically pure” grade, >99.5%) was ground in the drum of a "sand" planetary mill with jasper balls using isopropanol as dispersant.
  • the drum was charged with 50 g of the powder oxide, 150 g of balls, and 45 ml of isopropanol. The procedure was carried out for 30 minutes at a drum speed of 110 rpm.
  • the charge of the drum included 25 g of the mixture 72.4 wt% Cu 2 O + 27.6 wt% SDC (18.1 g Cu 2 O and 6.9 g SDC), 50 g of balls and 25 ml of iso- propanol. The procedure was carried out for 50 minutes at a speed of 80 rpm, and for 10 minutes at 110 rpm.
  • the dispersant was removed in oven at 100°C, and the Cu 2 O-SDC mixture added with a 5 wt% aqueous solution of polyvinyl alcohol (PNA) as binder (10% of the powder mass).
  • PNA polyvinyl alcohol
  • a heat treatment was performed at 800°C with a 1.5 hour isothermal holding time and air blasting.
  • the pellets were heated and cooled at a rate of 250°C/hour. After the heat treatment, the pellets changed color from brown to black.
  • the diameter shrinkage and the geometrical density of the sintered pellets were 1.7% and 4.05 g/cm respectively.
  • the pellets were broken in a jasper mortar to obtain grains ⁇ 1.25 mm in size.
  • the coarse-grain powder was ground in a "sand" planetary mill with jasper balls in the presence of isopropyl alcohol. The charge of the mill drum did not exceed 2/3 of their volume.
  • the powder/dispersant ratio was maintained at ⁇ 1:0.95.
  • the fine powder was used to prepare a slurry.
  • the powder mixture of A. was ground in the drum of a "sand" planetary mill with jasper balls.
  • Polyvinyl butyral (PNB) was used as binder and ethanol as the dispersant.
  • the charge included 20 g of the powder mixture, 8 ml of 5 wt% solution of PNB in ethanol, and 15 ml of ethyl alcohol.
  • the charge was mixed for 30 min at a speed of 80 rpm.
  • the resulting slurry was poured into a vessel outfitted with a tight cover to prevent evaporation of the dispersant.
  • the slurry of B. was brushed onto an SDC electrolyte membrane (1.82 mm-thick) while stirring.
  • An amount of 16 ⁇ 4 mg/cm (corresponding to a thickness of 65+5 ⁇ m) of "raw" pre-cermet was applied by three brushings with intermediate drying in a warm air jet.
  • the pre-cermet/electrol te membrane assembly was then heated in air at 1050°C under the following conditions: heating at a rate of 200°C/hour in the interval from 20 to 500 °C and at a rate of 250°C/hour in the interval from 500°C to the experimental temperature.
  • the pre-cermet/electrolyte membrane assembly was kept under isothermal conditions for 2 hours at the final temperature, then cooled at a rate 200 °C/hour.
  • the final thickness of the pre-cermet layer in the pre-cermet/electrolyte membrane assembly was 42 ⁇ m and the thickness shrinkage was 38.7% pointing for a good sintering of the pre-cermet structure.
  • the density of the "raw” and heat treated pre-cermet layer accounted for 45% and 64% of the design density, respectively. So, the open porosity of the heat treated pre-cermet before reduction was ⁇ 36%.
  • the porosity value was also evaluated by mercury porosimetry. Heat-treated pre-cermet material was deposited on ten plates of SDC electrolyte to a total mass of 0.448 g. The experiments were carried out on PA-3M mercury porosimetric installation, and the volume normalized for 1 g of pre-cermet material was 0.0776 cm 3 . The volume porosity was then calculated from the following equation: where mQuOx an d m SDC indicate the relative weight amount of the phases in the pre- cermet, and dQuOx and dsDC me specific densities of Cu 2 O (6 g/cm 3 ) and SDC (7.13 g/cm ) phases.
  • the measured volume porosity was 34 ⁇ 3%, which is in agreement with the porosity estimated from mass and geometric values.
  • the average size of the pores was seen to be 1 ⁇ m.
  • the pre-cermet of the pre-cermet/electrolyte membrane assembly of C. was reduced at a temperature of 500°C (at a rate of 200°C/hour).
  • the oven was conditioned with argon (3 vol.% H 2 O), then hydrogen (3 vol.% H 2 O) was introduced to replace argon and kept for 40 min.
  • Figures 3 a and 3b are two micrographs of the outer surface of the cermet, respectively in secondary electron emission mode (figure 3a) and in backscattering mode (figure 3b). From these two pictures it can be seen that the prepared cermet has a porous structure where both phases (Cu and SDC) are intimately mixed and homogeneously distributed.
  • the above described method cannot be used to determine the cermet porosity after reduction.
  • Dm is the mass difference between the copper and copper oxide
  • dcuO and d u are, respectively the density of copper oxide (6 g/cm for Cu 2 O) and metallic copper (8.9 g/cm 3 ).
  • DN 0.0532 cm 3 .
  • Pre - Cermet ( ox ) V SDC ( X) + V CuO ⁇ ( ⁇ x) + V p0 ,. e ( ⁇ X) (3)
  • N pore (red) V pore (ox) + AV (6)
  • the specific surface area was determined by the nitrogen BET method (Sorpty 1750, Carlo Erba Stramentazione, Italy) and resulted to be 1.6 m 2 /g. F. Measurement of the Electrical Resistance of the Cu-SDC cermet anode.
  • the layer resistance (measured along the major layer axis) of the cermet anode was measured by dc four-probe method using an EC-1286 device (Solartron Schlumberger).
  • the cermet anode had a surface of lxl cm and was 42 ⁇ m-thick. Current and potential probes were made of platinum wire.
  • the sample was further heated in hydrogen (3 vol.% H 2 O) up to 700°C at a rate of 200°C/hour. The temperature was maintained for 2 hours, then sequential measurements of resistance were done and the stability of the cermet anode was ascertained.
  • the sample was cooled to 500°C by steps of 50°C at a rate of 100°C/hour and step time of 10 min, and its resistance was measured at each grade. Finally, the sample was cooled at a rate of 200°C/hour to room temperature and its resistance was measured again.
  • the results are shown in Figure 2.
  • the cermet anode has a metallic behavior with a resistance increasing with temperature. This reads for a uniform distribution of the metallic phase through the cermet anode.
  • the electric resistance longitudinally along the cermet anode changes between 6.3 m ⁇ and 21.0 m ⁇ at a temperature from 20 to 700°C (as from Table 2).
  • the specific electrical conductivity along the anodes is 11905 Scm " and this value confirms that the electric characteristics of the cermet anode are better than those of previously disclosed cermet anode.
  • a three-electrode cell (1) as from Figure 5 was used.
  • the cell comprised a cermet anode (2) as from the present examples, an electrolyte membrane (3) of Ce 0 ⁇ 8 Sm 0 . 2 O 9 (samaria-doped ceria, SDC), and a cathode (4) of Pt+PrO x .
  • a fine Pt+PrO x paste was painted as cathode (4) on the surface of the electrolyte membrane (3) opposite to that in contact with the anode (2) (IHTE RAS, SU invention certificate No. 1.786.965).
  • a reference electrode (5) was made of a platinum coil on the circumference of the electrolyte membrane (3).
  • the three-electrode cell was pressed by a spring load against the rim of a zirconium dioxide tube (6).
  • Hydrogen fuel gas (98 vol.% H 2 + 3vol.% H 2 O, N H2 -2-5 1/hour) was fed to the anode side through an alumina tube (7) positioned inside the zirconium dioxide tube (6).
  • the composition of the combusted cermet anode was determined by means of a solid electrolyte oxygen sensor (8).
  • the cell temperature was measured by a chromel-alumel thermocouple (9).
  • the overvoltage of the electrodes and the ohmic voltage drop in the electrolyte were determined under stationary conditions (galvanostatic mode) by the current interruption method.
  • the length of the current interruption edge did not exceed 0.3 ⁇ s.
  • the off- current state time of the cell was -0.3 ms (millisecond).
  • the relative duration of the cut- off pulses (off/on) was ⁇ 1/1540.
  • the measuring set-up included the following instruments:
  • the same preparation procedure as described in example 1 was applied using CuO in the place of Cu 2 O and the following amount of starting materials: CuO (18.7 g) and SDC (10).
  • the ground CuO had a specific surface area (S Cu0 ) of 0.9 m 2 /g and an average particle size (d Cu0 ) of 3.4 ⁇ m at a normal particle size distribution from 0 to 20 ⁇ m.
  • the density of the applied slurry and pre-cermet accounted for 45% and 56% of the design density respectively.
  • the open porosity of the pre-cermet before reduction to cermet was 44%, and that of the cermet was 60%.
  • the specific surface area of the cermet was 1.81 m /g.
  • the electrical resistance along the cermet anode and the specific electric conductivity were measured according to example 1.
  • the results are set forth in Table 2 and show that the electric characteristics of the cermet anode are better than those of previously disclosed cermet anode.
  • Figure 4 shows anodic polarization curves at 650°C for the cermet anodes of example 1 and 2. Relative high current densities are obtained with low anodic overpotentials, as a consequence of the high conductivities and porosity of the anodes.

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Abstract

L'invention concerne une pile à combustible à oxyde solide dans laquelle l'anode comprend un cermet contenant une partie métallique et une partie de matière céramique d'électrolyte interdispersées de manière sensiblement uniforme.
EP03808290A 2003-12-24 2003-12-30 Pile a combustible oxyde solide Withdrawn EP1711977A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03808290A EP1711977A1 (fr) 2003-12-24 2003-12-30 Pile a combustible oxyde solide

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PCT/EP2003/014999 WO2005064717A1 (fr) 2003-12-24 2003-12-24 Pile a combustible a oxyde solide
EP03808290A EP1711977A1 (fr) 2003-12-24 2003-12-30 Pile a combustible oxyde solide
PCT/EP2003/014984 WO2005064732A1 (fr) 2003-12-24 2003-12-30 Pile a combustible a oxyde solide

Publications (1)

Publication Number Publication Date
EP1711977A1 true EP1711977A1 (fr) 2006-10-18

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Family Applications (1)

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EP03808290A Withdrawn EP1711977A1 (fr) 2003-12-24 2003-12-30 Pile a combustible oxyde solide

Country Status (1)

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EP (1) EP1711977A1 (fr)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005064732A1 *

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