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WO2000069008A1 - Cellule électrochimique - Google Patents

Cellule électrochimique Download PDF

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Publication number
WO2000069008A1
WO2000069008A1 PCT/DK2000/000228 DK0000228W WO0069008A1 WO 2000069008 A1 WO2000069008 A1 WO 2000069008A1 DK 0000228 W DK0000228 W DK 0000228W WO 0069008 A1 WO0069008 A1 WO 0069008A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
cell
carrying electrode
sintering
carrier 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.)
Ceased
Application number
PCT/DK2000/000228
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English (en)
Inventor
Mette Juhl JØRGENSEN
Carsten Bagger
Søren Primdahl
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Riso National Laboratory
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Riso National Laboratory
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 Riso National Laboratory filed Critical Riso National Laboratory
Priority to AU43919/00A priority Critical patent/AU4391900A/en
Publication of WO2000069008A1 publication Critical patent/WO2000069008A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
    • 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
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to an electrochemical cell, such as a fuel cell, and comprising a porous, carrying electrode structure, optionally including several layers, on which an electrolyte and another electrode are deposited, where the carrying electrode structure and the electrolyte are sintered together, for instance an Ni/YSZ anode including several layers and where a YSZ electrolyte and a cathode are deposited thereon.
  • Such an electrochemical cell with an oxygen- ionic conducting, gasproof electrolyte can be driven as a fuel cell, as fed reducing and oxidizing gases are caused to provide an electrical current to be utilized.
  • the cell can be operated by a power causing oxygen to be removed from the gas at one electrode and fed to the gas at the other electrode.
  • water can be electrolysed on the first electrode, and/or oxygen can be accumulated on the second electrode.
  • the oxygen fed to the second electrode can be caused to react with the present gas .
  • the efficiency of the fuel cell can be restricted inter alia by the conductivity and thickness of the electrolyte. Therefore the efficiency and the output of the cells can be improved by minimizing the thickness of the electrolyte.
  • the electro- lyte has usually been the structurally carrying component of the cell, and therefore a typical electrolyte thickness of 100 to 200 ⁇ m has been used.
  • the thickness of the electrodes is typically 20 to 100 ⁇ m. The minimizing of the electrolyte thickness is particularly important at low operational temperatures, such as 700 to 850 °C.
  • the basic requirements to the electrolyte are inter alia gas density without through pores as well as a high conductivity, and accordingly a predetermined purity of the material is required. It is assumed that the electrodes are preferably porous whereby the access for gases to and from the active centres inside the electrode are not reduced by diffusion barriers.
  • the entire cell including an electrolyte and two elec- trodes must be reasonably plane and of a uniform thickness in order to be stacked in a series connection of cells, a so-called stack. In addition, each cell must be sufficiently strong for tolerating handling and mounting procedures.
  • the manufacture of a structurally carrying component of a material like the material of an electrode ensures a high degree of freedom with respect to the thickness of the electrolyte.
  • the hitherto known carrying electrode structures are of a thickness of 0.7 to 2 mm. Such a structure is to a certain degree encumbered with draw-backs both with respect to the amount of material used and with respect to the restricted gas flow through the porous structure, viz. the diffusion barrier.
  • films of the electrolyte material and the carrier structure material on the basis of a slurry of particles (a slip) by inexpensive, scalable and wet ceramic processes, such as film casting, viz. tape casting. These films can be cast directly atop one another or separately and be laminated by way of rolling. Subsequently, the two layers must be sintered together. If the carrier structure and the electrolyte do not substantially shrink to the same extent during the sintering, stresses arise in the entire material and cause deformations. Therefore it is very important to adjust the shrinkage during the sintering of the two structures. The latter is complicated by the fact that the electrolyte must be gasproof as mentioned above whereas the carrier structure must be porous.
  • the particle layer can be subjected to a dense sintering without involving formation of pinholes provided said particle layer is so thick that after the sintering it forms an electrolyte of a thickness of more than approximately 40 ⁇ m.
  • the difference in the thermal coefficients of expansion of the two structures plays a role in determining how thick the electrolyte layer can be relative to the carrier structure without inducing too high stresses in said layer.
  • the situation can be further complicated by the presence of an intermediate electrode structure.
  • the electrolyte layer is made very thin, such as less than 10 ⁇ m, a risk is, however, involved of the electronic conductivity of said electrolyte being increased by the diffusion therein especially of Mn from the cathode side.
  • An increase of the electronic conductivity corresponds to a short-circuit and is damaging to the fuel cell.
  • cations can be repositioned in the electrolyte structure during the passage of an electric current. The latter can affect the conductivity of the material, and the problem is increased proportional to a decreasing electrolyte thickness because the potential gradient is accordingly increased. The latter is in particular to be seen in the light of an expected operation period of 40 to 50,000 hours.
  • extreme requirements are in addition presented to a perfect particle packing in the layer which is to form the electrolyte.
  • the object of the invention is to show how it is possible in a very cost-effective manner to manufacture a structure with a carrier structure and an electrolyte presenting the required properties.
  • a controlled composition of the materials forming part of the carrier structure it is possible to manufacture a gasproof, thin electrolyte on a carrier structure by way of simple and cost-effective processes suited for mass production.
  • the articles produced must furthermore present a sufficient porosity in the carrier structure and a gasproof electrolyte, be plane without crackles and in addition be very sturdy.
  • An electrochemical cell of the above type is according to the invention characterised in that the carrier electrode structure and the electrolyte are manufactured directly atop one another without involving an assembling process prior to the sintering, that the thickness of the carrier structure is less than 700 ⁇ m, preferably less than 500 ⁇ m and especially less than 300 ⁇ m, and that the thickness of the electrolyte deposited thereon is between 10 and 40 ⁇ m, preferably between 10 and 25 ⁇ m and especially between 15 and 25 ⁇ m, as a sintering -promoting substance and an air-entraining substance as well as a contraction-controlling substance can be added to the carrier structure.
  • the entire resulting structure can be manufactured without assembling steps by way of sintering at 1250 to 1400 °C.
  • a half-cell which can be manufactured in one process, is sturdy and presents a high efficiency, a low waste percentage during the manufacture as well as a reduced material consumption, and which in addition is scalable.
  • an independent half-cell is obtained which is particularly suited for mass production in large dimensions.
  • the sintering together viz. the sintering of the electrolyte layer and the permanent carrier structure with said electrolyte layer deposited on the carrier structure, implies in addition that a particle packing is obtained which is sufficiently perfect for not forming pinholes.
  • the carrier structure and the electrolyte may according to the invention be manufactured directly atop one another without involving an assembling process prior to the sintering, and a contraction-controlling substance may have been added to said carrier structure.
  • the contraction-controlling substance may, if desired, be formed by a sintering -promoting substance, such as Mn in an amount of 0.05 to 25 metal atom% , preferably 0.05 to 10 metal atom% and especially 0.1 to 5 metal atom% in order to obtain a sufficient, uniform sintering shrinkage of the carrier structure and the electrolyte.
  • fig. 1 is a cross sectional view of a carrier structure with an electrolyte applied thereon, viz. a so-called half-cell, and with and without a functional electrode layer,
  • Fig. 2 is a cross sectional view of an electrochemical cell including a half-cell, cf. Fig. 1, with a cathode applied thereon,
  • Fig. 3 is a cross sectional view of a set-up for an electrical characterization of an electrochemical cell with a platinum net applied onto the cathode surface and onto the surface of the carrier structure, said cell being mounted between some gas distribution plates which in turn are coupled between two sets of concentric aluminium pipes, gases being fed through the outer pipe and leaving through the inner pipes,
  • Fig. 4 illustrates two sets of measuring data, each set including area-adjusted cur- rent-voltage curves, the DC resistance of the cell corresponding to the negative inclination,
  • Fig. 5 is a cross sectional view of a symmetrical measuring device with two identical carrier structures and two identical functional electrode layers and an intermediate electrolyte, where the measuring device is contacted between two platinum balls with their respective platinum conductors,
  • Fig. 6 shows measuring data in form of two impedance spectra after adjustment for electrode area and electrolyte resistance, where the squares correspond to carrier structures without air-entraining substances, and circles correspond to corresponding articles including 40% by volume of corn starch, viz. 9.5 % by weight, in the carrier structure,
  • Fig. 7 shows an equivalent circuit for interpretation of the measuring data of Fig. 6, where L is inductance, R s is a series resistance in the electrolyte, R P is the polarisation resistance of the electrode, R D is the diffusion resistance inside the carrier structure and outside said structure, and Q are constant phase elements representing a non- ideal capacitance associated with the said resistances,
  • Fig. 8 is a sectional view through the half-cell of Fig. 1 with metal plates glued thereon, said metals plates comprising towing eyes for a strength test in connection with a uniaxial pull,
  • Fig. 9 shows measuring data for the tensile strength of the half-cell at room temperature
  • Fig. 10 shows dilatometric curves measured on cylinders of non-sintered sheets of a tape-cast electrolyte and carrier structure. The shrinkage of the articles during the sintering appears from the curves. 1) sheet of carrier structure without a sintering-promoting substance, 2) sheet of carrier structure admixed 3.5 metal atom% MnO 2 as sintering-promoting substance, 3) sheet of electrolyte material.
  • a gasproof, thin electrolyte 1 is provided on the surface of a porous carrier structure 3, cf. Fig. 1. Since the electrolyte layer 1 is made thin, the electric resistance in said layer is reduced and the efficiency of the completed half-cell is increased. It is also desired to maintain a predetermined thickness of the electrolyte 1 in such a manner that said electrolyte is totally tight during an industrial manufacturing. The thickness should furthermore be such that expectable pollutions of the electrolyte 1 during operation do not cause a through electron conductivity and consequently a short-circuiting of the completed half-cell. Accordingly, attempts have been made at providing an industrial manufacturing technique rendering it possible to allow an electrolyte thickness of the magnitude 10 to 40 ⁇ m. As a result, it is also possible to obtain a predetermined material reduction and a predetermined reduction of the production price.
  • the production price of the cell can be further reduced by minimizing the thickness of the carrier structure 3 because material reductions and reduced diffusion paths through the structure are obtained for the reacting gases.
  • the latter should, however, be weighed or balanced against the total strength of the component, inter alia because a predetermined porosity in the carrier structure 3 is desired.
  • the entire electrochemical cell is here in form of a fuel cell, such as an SOFC fuel cell, and includes a gasproof electrolyte 1 surrounded by two porous electrodes, cf. Fig. 2.
  • One electrode can operate as a carrier structure 3 for the cell or form part of said carrier structure.
  • a functional electrode layer 4 is inserted between the carrier structure 3 and the electrolyte 1. cf. Fig. 1A.
  • the functional electrode layer 4 ensures an electrochemical conversion of reactants whereas the carrier structure 3 both reinforce the cell and operates as a current collector.
  • the cell is made of the following materials:
  • Carrier structure (anode): A mixture of NiO and yttrium-stabilized zirconia (YSZ), where NiO is reduced to Ni during operation of the fuel cell. MnO 2 is added as sintering-promoting substance.
  • Functional electrode layer A mixture of NiO and YSZ.
  • Electrolyte YSZ.
  • Cathode A mixture of lanthane strontium manganite (LSM) and YSZ.
  • YSZ can as electrolyte for instance be replaced by an oxygen-ionic conducting ZrO 2 doted with a combination of Sc, Y and other elements.
  • the YSZ-fraction in the carrier structure 3 can, if desired, be replaced by another strength-providing material, such as A1 2 D 3 or ZrO 2 or a combination thereof, optionally admixed one or more dopants.
  • the layer dominating with respect to thickness in the carrier structure can, if desired, include ZrO 2 , which has been partially stabilized with other oxides to such an extent that martensitic phase transformation can occur at the handling and mounting temperatures of the cell.
  • the stabilizing oxide can optionally be Y 2 O 3 in an amount of 8 mol% , especially less than 5 mol% .
  • Ni as electrically conducting material in the carrier structure can also be replaced by other electronic conductors.
  • Other additives including Mn can be used as sintering-promoting substance.
  • the cathode 6 can also operate as the carrier structure.
  • Binder Poly vinyl butyral
  • Air-entraining substances Corn starch or a surplus of the above organic auxiliary materials.
  • auxiliary materials can, however, be replaced by other materials decomposing or oxidizing during the sintering without leaving substances detrimental to the properties of the structure.
  • the electrolyte material is suspended in a solvent.
  • Organic auxiliary materials are added, such as a dispersant, a binder, a softener and a slip.
  • the suspension is subjected to a ball grinding.
  • the slip is evacuated and subjected to a filtering prior to the moulding. Slips for the manufacturing of the carrier structure and for the spraying of the functional electrode layer, respectively, are manufactured in a similar manner.
  • the electrolyte slip is cast on a carrier substrate, viz. a silicon-coated Mylar sheet.
  • a carrier substrate viz. a silicon-coated Mylar sheet.
  • Other sheets can, however, also be involved in connection with the tape casting.
  • the functional electrode layer is sprayed onto the electrolyte sheet.
  • the carrier structure of the cell is manufactured on the electrolyte sheet with the functional layer 4.
  • articles are cut out in desired sizes for sintering.
  • a slip for manufacturing the carrier structure 3 of the cell is manufactured as described under I.
  • the slip is moulded on a carrier substrate 3, viz. a silicon-coated Mylar sheet, whereafter the sheet is dried.
  • Other sheets can, however, also be involved.
  • the slip for the airborne spraying of the functional electrode layer 4 and the electrolyte is manufactured as described under I.
  • the functional electrode layer 4 is sprayed onto the cast carrier structure sheet either before or after the cutting of the sheet. After the drying, the electrolyte is sprayed thereon, and the cut out articles are subjected to a sintering.
  • Both manufacturing methods involve a sintering of the articles at 1250 to 1400°C, typically at 1300°C for 12 hours.
  • the articles are typically placed on a porous ceramic support, and they can, if desired, be covered by a corresponding plate.
  • the sheet moulding can in principle be replaced by methods such as serigraphy, rolling or extrusion, whereas the airborne spraying can be replaced by for instance serigraphy, electrostatic spraying, swabbing or immersion.
  • a functional electrode layer can, if desired, be omit- ted between the carrier structure 3 and the electrolyte 1.
  • the slip for manufacturing the carrying cell structure can, if desired, be admixed a sintering-promoting substance, such as MnO 2 , in order to adjust the sintering shrinkage to the shrinkage of the electrolyte.
  • Mn or MnO 2 can advantageously be added in amounts of from 0.05 to 25 metal atom% , preferably 0.05 to 10 metal atom% and especially 0.1 to 5 metal atom% to the carrier structure in order to obtain a uniform sintering shrinkage of the carrier structure and the electrolyte.
  • the shrinkage and the porosity of the carrier structure can be adjusted by a suitable calcination and crushing of the materials forming part of the carrier structure, and by an addition of organic auxiliary materials or air-entraining substances.
  • Square articles were manufactured with the dimensions of up to 12 times 12 cm 2 as well as round articles of a diameter of 12 cm.
  • a scaling from 5 times 5 cm 2 to 12 times 12 cm 2 involved no particular problems, and further scalings are possible.
  • the described methods can be used directly for mass production.
  • the half-cell according to the invention is manufactured by cost-effective procedures as the ceramic techniques used are simple and scalable. No cost-intensifying additional operations for assembling the carrier structure and the electrolyte are involved.
  • the carrier structure, the electrolyte and an optionally functional electrode layer are sintered together, which reduces the number of sintering steps compared to a separate sintering of each element.
  • the thickness of the carrying electrode structure is less than 700 ⁇ m, preferably less than 500 ⁇ m, especially less than 300 ⁇ m.
  • the thick- ness of the electrolyte is between 10 and 40 ⁇ m, preferably between 10 and 25 ⁇ m, especially between 15 and 25 ⁇ m.
  • the carrier structure is made thin and porous while maintaining the necessary strength and a suitable electrolyte thickness.
  • a fuel cell is manufactured with an electrolyte shaped by way of sheet moulding of YSZ with 8 mol% Y 2 O 3 .
  • a functional electrode layer is applied onto the cell, said electrode layer including 56% by weight of NiO and 44% by weight of YSZ with 8 mol% Y 2 O 3 by means of an airborne spraying.
  • the carrier structure includes 56% by weight of NiO and 44 by weight of YSZ with 3 mol% Y 2 O 3 , to which 3.5 metal atom% of MnO 2 are added as sintering-promoting substance.
  • the carrier structure is sheet moulded onto the functional layer.
  • the component including the electrolyte, the functional layer and the carrier strucmre is punched out.
  • the component is sintered between two porous ceramic plates at 1300°C for 12 hours. Subsequently, the thickness of the carrier structure, the functional anode layer and the electrolyte is approximately 200 ⁇ m, 10 ⁇ m and 15 ⁇ m, respectively.
  • a cathode with a functional layer of LSM and YSZ as well as a current-collecting layer of LSM is applied by way of airborne spraying and sintered at 1100°C for two hours.
  • the efficiency of the cell is characterised as follows, cf. Fig. 3.
  • the cell has been efficiently contacted where it is covered by the platinum grid.
  • the cell with the contacting is mounted between two plane gas distribution plates 10 with openings and ribs which ensure gas access to the electrodes.
  • the cell and the contacting and the gas distribution plates 10 are mounted between two sets of alumina pipes 11, 12 in an oven, cf. Fig. 3.
  • the cell is heated to a temperature of 1050 °C.
  • the temperature is measured by means of thermocouples arranged 1 mm above the centre of the cell.
  • the cathode side is fed with air, whereas the anode side is fed with hydrogen moistened with 2% water.
  • the gases are fed through the outer pipes 11 and removed through the inner pipes 12.
  • the voltage across the cell can be measured at the edge V ⁇ and the centre V c of the electrodes.
  • Current is collected on the cell through the platinum grids and separate conduits by loading with external resistances, and current-voltage curves, cf. Fig. 4, are taken at the edge and the centre, respectively.
  • the negative inclination of the current-voltage curves correspond to the DC resistance of the cell.
  • an area-specific internal resistance of 0.42 ⁇ cm 2 is obtained at 860 °C with hydrogen saturated with 2% water and air on the anode and the cathode side, respectively.
  • the cell voltage in the unloaded state corresponds to the theoretical voltage between the present gases at the operational temperature, which shows that the electrolyte is gasproof.
  • the completed article is strong and flexible.
  • the latter can be illustrated by a loss of less than 10% being determined during the sintering and the handling of the sintered article, which includes the carrier structure and the electrolyte, said loss being determined during the further manufacture of the cell.
  • Such a loss is very small compared to typical losses during the manufacture of composite ceramic components.
  • the gas density of the electrolyte is verified by application of a colour penetrant (diamant fuchsine) and a redrying thereof, which in case of sintering errors or pores is absorbed and leaves a distinct discoloration.
  • a colour penetrant diamant fuchsine
  • a fuel cell is manufactured by way of sheet moulding or tape casting of a carrier strucmre including 56% by weight of NiO and 44% by weight of YSZ with 3 mol% of Y 2 O 3 , which has been admixed 3.5 metal atom% of MnO 2 as sintering-promoting substance.
  • a functional electrode layer including 56% by weight of NiO and 44% by weight of YSZ with 8 mol% of Y 2 O 3 is applied by way of airborne spraying.
  • An electrolyte of YSZ with 8 mol% of Y 2 O 3 is sprayed thereon.
  • the half-cell is sintered between two porous ceramic plates at 1300°C for 12 hours. Subsequently, the thickness of the carrier strucmre, the functional anode layer and the electrolyte is approximately 200 ⁇ m, 10 ⁇ m and 15 ⁇ m, respectively.
  • a cathode with a functional layer of LSM and YSZ as well as a current-collecting layer of LSM is applied onto the electrolyte by way of airborne spray- ing and sintered at 1100° C for two hours.
  • Example II an area-specific internal resistance of 0.40 ⁇ cm 2 is obtained at 890 °C with hydrogen 2% water and air on the anode and the cathode side, respectively.
  • the cell voltage in the unloaded state corresponds to the theoretical voltage between the present gases at the operational temperature, which shows that the electrolyte is gasproof.
  • the completed article is strong and flexible.
  • the latter can be illustrated by a loss of less than 10% being determined during the sintering and the handling of the sintered article, which includes the carrier strucmre and the electrolyte, said loss being determined during the further manufacture of the cell.
  • Such a loss is very small compared to typical losses during the manufacture of composite ceramic components.
  • the gas density of the electrolyte is verified by application of a colour penetrant (diamant fuchsine) and a redrying thereof, which in case of sintering errors or pores is absorbed and leaves a distinct discoloration.
  • a colour penetrant diamant fuchsine
  • a suitable addition of Mn0 2 and other measures changing the sintering shrinkage of the carrier structure render it possible to adjust the shrinkage of the carrier strucmre to the sintering shrinkage of the electrolyte.
  • the requirement to the same shrinkage is significantly increased at a scaling of the size of the sintered article.
  • Example 1 Yet another functional electrode layer as described in Example 1 is sprayed onto a non-sintered article as described in Example I, and yet another carrier strucmre is sheet moulded as described in the Example.
  • This symmetrical article is punched out in a size of 5*5 mm 2 and subjected to a sintering at 1300°C for 12 hours.
  • the edges of the article are subjected to a grinding so as to ensure that short-circuits do not occur across the edge of the electrolyte layer 1, cf. Fig. 1.
  • the manufacmred cells are mounted between four platinum wires 6 arranged such that two are positioned on the central portion of each electrode surface, cf. Fig. 5.
  • the cells are placed in an oven in a controlled atmosphere of hydrogen moistured with 3 % water.
  • the impedance of the cells is measured by impedance spectroscopy at 850 °C.
  • the measuring data are indicated as squares in Fig. 6.
  • a curve fitting of the impedance measurements was performed by means of the program "Equivalent Circuit” , with an equivalent circuit being adjusted to the measured data of Fig. 6.
  • the equivalent circuit includes capacitances C, inductances L, resistances R and constant phase elements Q.
  • the strength of the cells is particularly important during the handling following the sintering, during the application of the cathode as well as during the assembling of the cells into a stack of cells. In all these situations and up to the reduction of the carrier strucmre during the operationalization, the strength of the cell is dictated directly by the properties of the half-cell.
  • Half-cells in the dimensions 1*9 cm 2 are manufacmred as described under I. These articles are connected by metal plates glued thereon and provided with towing eyes 8 at both ends, cf. Fig. 8.
  • the electrolyte surface can optionally be micro-corrugated or rough in order to increase the surface and improve the physical adhesion of an electrode.
  • the half-cell viz. the carrier structure, optionally the electrode structure and the electrolyte, can be corrugated so as to be able to tolerate temperature gradients across the extension of the cell.

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Abstract

Cette cellule électrochimique solide comprend une structure poreuse (3) porteuse d'une électrode pourvue d'un électrolyte et comportant une autre électrode. La structure porteuse d'électrode (3) et l'électrolyte (1) sont frittés ensemble. Les cellules électrochimiques connues sont exploitées à environ 1000 °C. Il est, toutefois désirable d'abaisser la température entre 700 et 850 °C. L'inconvénient est que la résistance caractéristique de l'électrolyte (1) augmente, ce qui exige une réduction de l'épaisseur de l'électrolyte d'environ 10 à 15 νm. L'anode tient alors lieu de couche porteuse. L'électrolyte (1) peut être coulé en bande ou vaporisé sur l'anode. Le produit fini doit, toutefois, être plat, ce que l'on obtient, dans le cadre de cette invention, du fait de la fabrication, directement l'un sur l'autre, de la structure porteuse d'électrode et de l'électrolyte et ce, sans avoir à recourir à une opération d'assemblage avant le frittage, par le fait que l'épaisseur de la structure porteuse d'électrode (3) est inférieure à 700 νm et par le fait que l'épaisseur de l'électrolyte (1) placé au-dessus est inférieure à 40 νm. Il est ainsi possible d'ajouter, le cas échéant, à la structure porteuse d'électrode une substance agissant sur la contraction. Il est possible de fabriquer toute la structure en une seule étape par frittage à une température comprise entre 1250 et 1400 °C. On obtient une demi-cellule robuste, très efficace, à faible pourcentage de rebut durant le processus de fabrication, à consommation de matériau réduite et qui, de plus, est évolutive. En d'autres termes, on obtient une demi-cellule indépendante se prêtant au mieux à une production de masse sous de grandes dimensions.
PCT/DK2000/000228 1999-05-07 2000-05-05 Cellule électrochimique Ceased WO2000069008A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43919/00A AU4391900A (en) 1999-05-07 2000-05-05 Electrochemical cell

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA199900623 1999-05-07
DKPA199900623 1999-05-07

Publications (1)

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WO2000069008A1 true WO2000069008A1 (fr) 2000-11-16

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Cited By (11)

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WO2001057945A1 (fr) * 2000-02-04 2001-08-09 Stichting Energieonderzoek Centrum Nederland Procede de fabrication d'un ensemble comprenant un electrolyte porte par une anode, et cellule ceramique comprenant cet ensemble
EP1639669A4 (fr) * 2003-06-09 2007-10-17 Saint Gobain Ceramics Pile a combustible a oxyde solide a base de zircone fondue
US7632586B2 (en) 2002-01-09 2009-12-15 Htceramix S.A. Solid oxide fuel cell positive electrode—electrolyte—negative electrode
WO2013093607A2 (fr) 2011-12-22 2013-06-27 Lipilin Aleksandr S Cellule planaire modifiée et pile de dispositifs électrochimiques basée sur ladite cellule, procédé de fabrication de ladite cellule planaire et de ladite pile, et moule utilisé pour la fabrication de ladite cellule planaire
US9065104B2 (en) * 2010-06-11 2015-06-23 Commissariat A L'energie Atomique Et Aux Energies Alternatives Process for manufacturing elementary electrochemical cells for energy- or hydrogen-producing electrochemical systems, in particular of SOFC and HTE type
CN104995502A (zh) * 2013-02-06 2015-10-21 南洋理工大学 用于测试电池的方法和被配置成测试电池的装置
US10236528B2 (en) 2016-07-18 2019-03-19 Northwestern University Three dimensional extrusion printed electrochemical devices
US10350329B2 (en) 2014-10-15 2019-07-16 Northwestern University Graphene-based ink compositions for three-dimensional printing applications
US10584254B2 (en) 2014-05-15 2020-03-10 Northwestern University Ink compositions for three-dimensional printing and methods of forming objects using the ink compositions
US10793733B2 (en) 2015-04-07 2020-10-06 Northwestern University Ink compositions for fabricating objects from regoliths and methods of forming the objects
CN119340406A (zh) * 2024-12-19 2025-01-21 西安稀有金属材料研究院有限公司 一种阳极支撑的固体氧化物燃料电池半电池阳极片的制备方法

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001057945A1 (fr) * 2000-02-04 2001-08-09 Stichting Energieonderzoek Centrum Nederland Procede de fabrication d'un ensemble comprenant un electrolyte porte par une anode, et cellule ceramique comprenant cet ensemble
US6663999B2 (en) 2000-02-04 2003-12-16 Stichting Energieonderzoek Centrum Nederland Method of fabricating an assembly comprising an anode-supported electrolyte, and ceramic cell comprising such an assembly
US7632586B2 (en) 2002-01-09 2009-12-15 Htceramix S.A. Solid oxide fuel cell positive electrode—electrolyte—negative electrode
EP1639669A4 (fr) * 2003-06-09 2007-10-17 Saint Gobain Ceramics Pile a combustible a oxyde solide a base de zircone fondue
US9065104B2 (en) * 2010-06-11 2015-06-23 Commissariat A L'energie Atomique Et Aux Energies Alternatives Process for manufacturing elementary electrochemical cells for energy- or hydrogen-producing electrochemical systems, in particular of SOFC and HTE type
WO2013093607A2 (fr) 2011-12-22 2013-06-27 Lipilin Aleksandr S Cellule planaire modifiée et pile de dispositifs électrochimiques basée sur ladite cellule, procédé de fabrication de ladite cellule planaire et de ladite pile, et moule utilisé pour la fabrication de ladite cellule planaire
CN104995502A (zh) * 2013-02-06 2015-10-21 南洋理工大学 用于测试电池的方法和被配置成测试电池的装置
CN104995502B (zh) * 2013-02-06 2018-02-27 南洋理工大学 用于测试电池的方法和被配置成测试电池的装置
US9995794B2 (en) 2013-02-06 2018-06-12 Nanyang Technological University Methods for testing a battery and devices configured to test a battery
US10584254B2 (en) 2014-05-15 2020-03-10 Northwestern University Ink compositions for three-dimensional printing and methods of forming objects using the ink compositions
US11459473B2 (en) 2014-05-15 2022-10-04 Northwestern University Ink compositions for three-dimensional printing and methods of forming objects using the ink compositions
US10350329B2 (en) 2014-10-15 2019-07-16 Northwestern University Graphene-based ink compositions for three-dimensional printing applications
US10793733B2 (en) 2015-04-07 2020-10-06 Northwestern University Ink compositions for fabricating objects from regoliths and methods of forming the objects
US10236528B2 (en) 2016-07-18 2019-03-19 Northwestern University Three dimensional extrusion printed electrochemical devices
CN119340406A (zh) * 2024-12-19 2025-01-21 西安稀有金属材料研究院有限公司 一种阳极支撑的固体氧化物燃料电池半电池阳极片的制备方法

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