CA1310061C - Method of bonding a conductive layer on an electrode of an electrochemical cell - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A dense, electronically conductive inter-connection layer 26 is bonded onto a porous, tubular, electronically conductive air electrode structure 16, optionally supported by a ceramic support 22, by (A) providing the air electrode surface, (B) forming on a selected portion of the electrode surface 24, without the use of pressure, particles of LaCrO3 doped with an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the particles have a deposit on their surface comprising calcium oxide and chromium oxide;
(C) heating the particles with the oxide surface deposit in an oxidizing atmosphere at from 1,300°C to 1,550°C, without the application of pressure, to provide a dense, sintered, interconnection material 26 bonded to the air electrode 16, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO3. A solid electrolyte layer 18 can be applied to the uncovered portion of the air electrode, and a fuel electrode 20 can be applied to the solid electrolyte, to provide an electro-chemical cell 10.

Description

13100~1 l 73661-25 A METHOD OF BONDING A CONDUCTIVE LAYER ON
AN ELECTRODE OF AN ELECTROCHEMICAL CELL

BACKGROUND OF THE INVENTION
Fleld of the Inventlon:
The present lnvention relates to a method of bondlng a conductlve lnterconnectlon layer on an electrode of a solld oxlde electrolyte, electrochemlcal cell.
Hlgh temperature electrochemlcal cells are taught by Isenberg, ln U.S. Patent No. 4,490,444. In these type of cells, typlfled by fuel cells, a porous support tube of calcla stablllzed zlrconla, has an alr electrode cathode deposlted on lt. The alr electrode may be made of, for example, doped oxldes of the perov-sklte famlly, such as LaMnO3. Surroundlng the ma~or portlon of the outer perlphery of the air electrode ls a layer of gas-tlght solld electrolyte, usually yttrla stablllzed zlrconla. A selected radial segment of the alr electrode is covered by an lntercon-nectlon materlal. The lnterconnectlon materlal may be made of a doped lanthanum chromlte fllm. Sugge~ted dopants are Mg, Ca, and Sr.
~30th the electrolyte and lnterconnectlon materlal are applled on top of the alr electrode by a modlfled chemlcal vapor deposltlon process, utlllzlng temperatures c~

131~61 2 54,174 of from 1,200C to 1,400C in a reducing atmosphere, with the suggested use of vaporized halides of zirconium and yttrium for the electrolyte, and vaporized halides of lanthanum, chromium, magnesium,~ calcium or strontium for the interconnection material, as taught by Isenberg, in U.S. Patent No. 4,597,170, and Isenberg et al., in U.S.
Patent No. 4,609,562.
It has been found, however, that there are certain thermodynamic and kinetic limitations in doping the interconnection from a vapor phase by a chemical vapor deposition process at 1,300C to 1,400C. The vapor pressures of calcium chloride, and strontium chloride, are lo~ at vapor deposition temperatures, and so, are not easily transported to the reaction zone at the surface of the air electrode. Thus, magnesium is the primary dopant used for the interconnection material. However, a magnesi-um doped lanthanum chromite interconnection, for example LaO 97Mgo 03CrO3, has a 12% to 14% thermal expansion mismatch with the air electrode and electrolyte materials.
Additionally, use of halide vapors at 1,300C to 1,400C, in a reducing atmosphere, at partial pressure~ of oxygen less than 10 4 atm., can interact with the air electrode material during the initial period of interconnection application. This causes, in some instances, air electrode leaching of main constituents, such as manganese, into the interconnection material, which can cause pos3ible destabi-lization effects.
In an attempt to solve some of these problems, Isenbsrg et al., in U.S. Patent No. 4,598,467, suggested applying a separate, vapor deposited interlayer of, for example, calcium and cobalt doped yttrium chromite, about 1 micron thick (0.001 millimeter), between the air electrode, and the interconnection material and electrolyte. Ruka, in U.S. Patent No. 4,631,238, in an attempt to solve intercon-nection thermal expansion mismatch problems, taught cobaltdoped lanthanum chromite, preferably also doped with magnesium, for example LaCrO,93Mg0~o3coo~o4o3~ p 1310~61 3 54,174 deposited interconnection material, using chloride vapors of lanthanum, chromium, magnesium, and cobalt. Component oxides, and other chemical forms which decompose to oxides upon heating, such as carbonates, oxalates, formates, and hydroxides, can also be mixed, pressed at approximatley 352.5 kg./cm.2 (34.475 MPa-Mega Pascals) and then sintered in an oven at approximately l,450C to form bars of the material.
None of these solutions, however, solve all the potential problems of thermal expansion mismatch, Mn leaching from the air electrode, and the limitations of the incorporation of dopants such as calcium, strontium, and other materials such as cobalt and barium by vapor deposi-tion, in a simple and economical fashion. Many of these problems appear to be associated with the chemical vapor deposition process itself.
Attempts to densify Lal_xSrxCro3, using solid state sintering, to form an electrode structure, are discussed by Groupp et al., J. Amer. Ceram. Soc., Vol. 59, No. 9-10, pp. 449-450 (1976). They noted that the material was difficult to fabricate by normal sintering techniques, primarily due to volatilization of Cr oxide compounds in oxidizing atmospheres. Compositions containing up to 20 mole% Sr were prepared by dissolving nitrates of the constituent La, Sr, and Cr cations in a ~olution of citric acid and ethylene glycol, followed by evaporation at 135C, to provide a glasslike resin, which was then calcined at 800C, to provide a La1 x~rxCrO3 material. Powder samples of this material, with distilled water as binder, were uniaxially pressed, at 2,115 kg./cm.2 (20.685 MPa), to provide discs of 55% to 60% of theoretical density, which were then sintered in the temperature range of from 1,600C
to 1,700C for 1 hour, at oxygen activities of from 10 12 to 10 11 atm., to provide compacts having maximum densities of 95%+-Meadowcroft et al., Ceram. Bull., Vol. 58, No. 6,pp. 610-612, 615 (1979), also recognized oxidation and 131~

4 54,174 vaporization problems with Sr or Ca doped LaCrO3 in air at over 1,600C. They mixed La203 and Cr203 with SrC03, in appropriate amounts, and prefired the mixture in air at 1,400C. The reacted powder wa~ then uniaxially and then isostatically pressed, and fired at 1,500C in air. The influence of substitutions on vaporization rate was studied for: La1_xsrxcrO3 (O<x<0.2); LaO 8SrO 2AlO.5Cro.503;
LaO 8SrO 2AlO.25Cro.7503; LaO 8MgO.2CrO3' and LaO.8cao.2Alo.25cro.75o3 The lowest vaporization rate was 0 achieved for the calcium aluminum containing material.
Ruka, in U.S. Patent No. 4,562,124, teaches a perovsXite-like air electrode material which closely matches the thermal expansion characteristics of support tubes and solid oxide electrolytes in fuel cells. These materials are said to be single phase solid solutions.
They are made by mixing the component powders, pressing over 70.5kg./cm.2 ~68.95 MPa), and sintering at from 1,400C to 1,800C for 1 to 4 hours. Materials made include LaO 3CaO 5ceO.2MnO3; LaO 7Sr0-3Mn3;
0.7 0.2 aO.1Mn3; LaO.35Cao 65Mn3; LaO 5CaO 5CrO3 and LaO 3CaO 5CeO 2CrO3. Air electrode application means are described a~ plasma spraying, and slurry dipping followed by sintering.
Other methods of making lanthanum and calcium chromium oxides have been tried. Alexandov et al., in U.S.
Patent No. 4,035,266 teach melt production of LaCrO3;
2 4 aO 5SrO.5Cr204, under the action of a high freguency generator, with a working output of 60 kW at 300 kHz. The melt is then cooled, to provide an ingot of the refractory reaction mixture useful for fuel cell cathodes.
None of these teachings provide low temperature formation of a lanthanum chromite structural element in an oxygen atmosphere, without pressure application, on high temperature-reduction degradable, fragile, lanthanum manganite air electrode material, in an electrochemical cell. It is an object of this invention to provide such a process.

131~
54,174 DISCLOSURE OF THE INVENTION
Accordingly, the present invention resides in a method of bonding a dense, electronically conductive la~er on a porous, electronically conductive electrode surface, characterized by the steps:
(A) providing an electrode surfac~, (B) form-ing, on a selected portion o the electrode surface, without the application of pressure, particles of LaCrO3 doped w1th an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the parti-cles have a deposit on their surface comprising calcium oxide and chromium oxide ln an amount effective to lower the sintering temperature of the doped LaCr03 particles, (C) heating the particles containing the oxide deposit in an oxidizing atmosphere at a temperature of from approxi-mately 1,300C to 1,550C, without the application of pressure, to provide a dense, sintered interconnection material intimately bonded to the electrode, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO3.
The weight ratio of calcium oxide: chromium oxide is rom approximately 0.4 to 9.0:1, and the weight ratio of calcium oxide + chromium oxide: doped LaCrO3 particles, is from approximately 0.005 to 0.10:1. The doped LaCrO3 particles will have a size of from approximately 0.1 micron to 15 microns diameter and will generally comprise a mixture of large and small particles.
Prior to and during sintering, the calcium oxide + chromium oxide coating, usually a CaO + Cr2O3 coating, melts, draws the doped LaCrO3 particles closer together, and aids low temperature sintering of the particles. This provides a 95%+ dense interconnection, with no vaporization of chromi-um from the particles, nor leaching of materials from the electrode.
The interconnection will also have a good thermal coefficient match with the electrode due to calcium inclu-sion. The calcium oxide-chromium oxide can be applied to ~ 31B~l 6 54,174 the doped LaCrO3 particles, for example, by adding the particles to a solution of calcium nitrate and chromium nitrate, and heating in an oxidizing atmosphere to decom-pose nitrate and form a calciu~ oxide and chromium oxide deposit.
Preferably, the electrode structure on which the coated, doped LaCrO3 particles are formed is a porous air cathode made of strontium doped lanthanum manganite, in the form of a tubular structure, optionally supported by a porous, stabilized zirconia support tube. Additional steps, including applying a solid electrolyte layer over the remaining portion of the air electrode, and applying a cermet fuel electrode anode over the electrolyte, will complete formation of an electrochemical cell. This method allows easy formation of the interconnection without use of vapor deposition or pressing steps, and lowers thermal expansion mismatch of the interconnection with the air electrode and electrolyte.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the invention can be more clearly understood, conventional embodiments thereof will now be deQcribed, by way of example, with reference to the accom-panying drawings, in which:
Figure 1 i8 a schematic sectional view of a preferred embodiment of a single, tubular electrochemical cell, showing the interconnection layer on top of a sup-porting electrode;
Figure 2, which best describes the invention, is a block schematic drawing of the preferred method of this invention; and Figure 3 shows an idealized microscopic view of the interconnection formation, with Figure 3(A) showing melting of calcium oxide + chromium oxide, and Figure 3(B) showing gain growth and sintering of doped LaCrO3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to Figure 1 of the Drawings, a preferred, tubular, electrochemical cell 10 is shown. The 7 54,174 preferred configuration is based upon a fuel cell system, wherein a flowing gaseous fuel, such as a mixture of hydrogen and carbon monoxide, is directed axially over the outside of the`cell, as indicated by the arrow 12, and an oxidant, such as air, or 2 indicated by the arrow 14, flows through the inside of the cell. Where the cell is as shown, oxygen molecules pass through the porous, electron-ically conductive electrode structure 16 and are changed to oxygen ions which pass through the electrolyte 18, to combine with fuel at the fuel electrode 20.
It should be noted that the following description of the prepared tubular configuration should not be consid-ered limiting. It should also be noted that the intercon-nection material of this invention, described hereinafter, could be applied to electrochemical cells other than fuel cells. The term "air electrode" as used throughout means that electrode which will be in contact with oxidant, and "fuel electrode" means that electrode that will be in contact with fuel.
The cell 10 can include an optional porous support tube 22. The support tube can be comprised of calcia stabilized zirconia, forming a porous wall approxi-mately one to two millimeters thick. The air electrode, or cathode 16 i~ a porous, composite metal oxide structure approximately 50 microns to 1,500 microns (0.05 millimeter to 1.5 millimeter) thick. It can be deposited on the support tube by slurry dip and sinter techni~ues, or extruded as a self-supporting structure. The air cathode is, for example, comprised of doped oxides or mixtures of oxides of the perovskite family, such as LaMnO3, CaMnO3, LaNiO3, LaCoO3, LaCrO3, and the like, preferably LaMnO3.
Preferred dopants are strontium, calcium, cobalt, nickel, iron, and tin, preferably strontium.
Surrounding most of the outer periphery of the air electrode 16 is a layer of gas-tight solid electrolyte 18, generally comprised of yttria stabilized zirconia about 1 micron to about 100 microns thick (0.001 millimeter to ~ 3 ~
8 54,174 0.1 millimeter). The electrolyte 18 is deposited onto the air electrode by well known, high temperature, vapor deposition techniques. In the case where electrolyte is to be deposited before the interconnection, a selected radial segment or portion 24 of the air electrode 16 is maske~
during electrolyte deposition and then a layer of a non-porous interconnection material 26 is deposited on this segment or portion 24. If the interconnection is to be deposited first then the electrolyte portio~ is masked initially.
The dense interconnection material 26, which preferably extends the active axial length of each elongat-ed cell 10 as shown, must be electrically conductive in both an oxidant and fuel environment. The gas-tight interconnection 26 is roughly similar in thickness to the electrolyte, about 30 microns to about 100 microns (0.03 millimeter to 0.1 millimeter). The interconnection should be non-porous (over about 95% dense) and preferably be nearly 99~ to 100% electronically conductive at 1,000C, the usual operating temperature of a fuel cell.
The interconnection must also have a coefficient of thermal exp~nsion close to that of the solid electro-lyte, and tho electrode onto which it is deposited, and the other components, including the support tube, if used. The u~ual interconnection material i~ doped lanthanum chromite, of approximately 20 microns to 50 microns (0.02 millimeter to 0.05 milllmeter) thickness. Usually, an electrically conductivo layer 28 is deposited over the interconnection 26. This layer 28 is preferably comprised of the same matorial as the fuel anode 20, nickel or cobalt zirconia cermet, and about the same thickness, 100 microns.
Undoped lanthanum chromite is not very useful as an electronic interconnection, due to its combination of marginal conductivity, mismatch of thermal expansion coefficient with the rest of the fuel cell components, and phaqe transition from orthorhombic to rhombohedral near 275C. In this invention, at least one of Ca, Sr, Mg, Ca, ; . ~, j .

.
-~

131~
9 54,174 Ba and Co is present as a dopant throughout the intercon-nection material 26.
The interconnection in this invention will be made from sintered particles of calcium and chromium coated La1 xMxCrO3, where M is a dopant element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, and x = 0.075 to 0.25. Ordinarily, sintering ~uch particulate materials in uncoated form requires substantial pressures, and temperatures of over l,700C, with substan-tial loss of Cr and/or chromium oxides from the latticestructure. Such loss would lower electrical conductivity.
By forming a combination calcium oxide + chromium oxide material, usually a CaO + Cr203 mixture, on the surface of the particles, it has been found that high density sinter-ing can be accomplished at a much lower temperature, withno loss of chromium constituents from the particles, and with complete elimination of pressing. The term "without application of pressure", as used herein, means without application of traditional uniaxial or isostatic pressing techniques.
Calcium oxide plus chromium oxide appears to provide a unique combination for depositing on doped LaCrO3 particles, because its melting point is below doped LaCrO3, chromium is already pre~ent in the particle lattice, and calcium is very effective to match thermal expansion coefficient~ to the air electrode. The term "sintering" as used herein, means heating below the melting point of the main constituent particles, to provide a mass of bonded particles which may or may not contain unconnected porosi-ty. The heating may cause some smaller particle incorpo-ration onto the larger particles present.
In the method of this invention, doped LaCrO3 particles, as described previously, having a particle size distribution of from 0.1 micron to 15 microns, preferably 0.5 micron to 10 microns diameter, are made or purchased.
Within these ranges, preferably, at least 80% of the p~rticles would be less than 10 microns, and at least 20%

1 3 ~

54,174 of the particles would be less than 1 micron. With the use of particles over 15 microns, densification without pres-sure will be difficult at 1,500C. Under 0.1 micron, homogeneous mixing with Ca-Cr constituents will be diffi-cult, and chromium oxide loss is possible upon heating.
These doped LaCrO3 particles are then added to a salt solution containing both Ca and Cr, preferably calcium nitrate, i-e-, Ca(N03)2.4~2o, plus chromium nitrate, i.e., Cr(N03)3.9H20. Other useful salt solutions include calcium chloride plus chromium chloride, and like salts which upon heat reaction or decomposition are capable of forming a calcium oxide-chromium oxide material. In the case of the nitrates, heating alone will drive off water and gaseous oxides of nitrogen, leaving the oxides. In the case of chlorides, the metal chloride is reacted to gaseous oxides of chlorine, gaseous HCl, and metal oxide, where the metal oxide remains deposited. The use of chlorides is less preferred, due to possible contamination of fuel cell components.
The starting materials should be added so that the weight ratio of calcium oxide: chromium oxide formed ater heating is from approximately 0.4 to 9.0:1, prefera-bly from 0.75 to 4.5:1, and the weight ratio of calcium oxide and chromium oxlde:doped LaCrO3 particles is from 25 approximately 0.005 to 0.10:1, preferably from 0.04 to 0.10:1. Less calcium oxide than 0.4:1 of chromium oxide, will not help match thermal coefficients of expansion between the interconnect and the air electrode. Either, more calcium oxide than 9.0:1 of chromium oxide or less than 0.4:1 of chromium oxide, will begin to upset the melt phase relationship between the two compounds so that there may not be complete melt coating of the doped LaCrO3 particles. With le~s oxido mixture than 0.005:1 of doped LaCrO3 particle~, low temperature sintering will be hampered. With more oxide mixture than 0.10:1 of doped LaCrO3 particles, much non conductive oxide will remain unincorporated into the LaCrO3 structure.

~, ~

~31~
11 54,174 In the case of adding doped LaCrO3 particles to an aqueous solution of calcium nitrate + chro~ium nitrate, a slurry will be formed, step 1 in Fig. 2 of the Drawings.
This slurry, preferably, will be applied to a designated area of the electrode, step 2 in Fig. 2 of the Drawings, such as the axial, radial segment 24 shown in Fig. 1 of the Drawings. The slurry can be brushed on, applied ~y a tape casting method, or by any other technique not requiring pressing the thin and fragile air electrode material. At this point, the nitrate composition coats the doped LaCrO3 particles.
The coated air electrode is then heated, first to drive off water, forming a deposit of fine calcium nitrate and chromium nitrate particles on the surface of the doped LaCrO3. Continued heating will drive off gaseous oxides of nitrogen, and form fine calcium oxide + chromium oxide particles on the surface of the doped LaCrO3. Such elimination of nitrogen containing gases will u~ually occur at approximately 400C to 800C, and may be accompanied by a temporary solid to liquid phase change. Such fine particles will be left on the surface of the doped LaCrO3, to the extent that a discontinuous or continuous coati~g is present, step 3 in Fig. 2 of the Drawings.
Then, the doped LaCrO3, with calcium oxide +
chromium oxide on its particles surface, is further heated to approximately l,050C to 1,250C, within which range molting of the calcium oxide + chromium oxide begins, completely covering the doped LaCrO3 particles, and flowing into voids or interstices between the the particles. After this, the temperature is raised to 1,300C to 1,550C, within which range additional melting may occur, and the doped LaCrO3 material near the calcium oxide + chromium oxide melt dissolve therein, solidifying some of it.
Smaller particles of doped LaCrO3 material are incorporated into larger because of their higher surface energy, so that their grain boundary substantially disappears. Any remain-ing melt solidifies on cooling.

~31~
12 54,174 In this process, the calcium and chromium from the melt are incorporated into the doped LaCrO3 particles, and gradually diffuse throughout the bulk of the doped LaCrO3 particl'es'. In this process, the doped LaCrO'3 particles sinter together at 1,300C to 1,550C, which is much lower than their normal sintering temperature, step 4 in Fig. 2 of the Drawings. Thus, particle "grain growth"
into the volume occupied by the calcium oxide + chromium oxide melt provides an almost complete densification without application of pressure. It is possible to form the interconnection on a green electrode, i.e., one not completely sintered, and then, sinter both the electrode and the calcium oxide plus chromium oxide coated, doped LaCrO3 interconnection particles at the same time. In all instances where heating occurs in this invention, it takes place in an oxidizing atmosphere such as air or 2 Figure 3(A), illustrating the previous discus-sion, is an idealized microscopic view of the interconnect formation, and shows calcium oxide + chromium oxide melt 30, coating and disposed between the doped LaCrO3 particles 31, and in voids 32 between particles. Figure 3(B) shows doped LaCrO3 partial dissolution and grain growth into the voids between particles at final sintering temperatures of 1,300C to 1,550C, and reduction of the void volume to provide high density material. As can be seen in Figures 3~A) and 3(B), voids 32 are greatly reduced, and remain disconnected and one smaller particle has been incorporated into a larger particle.
In addition to in-situ formation of doped LaCrO3 coated with calcium oxide + chromium oxide on the elec-trode, where the deposit of calcium oxide + chromium oxide is formed by mixing the doped LaCrO3 with a salt solution compri~ing calcium and chromium, followed by heating the mixture to form the oxides; the slurry of calcium + chromi-um salt solution plus doped LaCrO3 particles can be appliedto a glass plate, or the liXe, dried, and heated to drive off oxides of nitrogen or halide and provide calcium oxide ... .

1 3 ~
13 54,174 I chromium oxide on the doped LaCrO3 particles. These particles can then be mixed with water or other fugitive liquid, and then applied to the electrode and sintered.
Thus, the coated, doped LaCrO3 particles can be "formed" on the electrode surface by a variety of means.
An additional forming method would involve plasma spraying the oxide coated, doped particles of LaCrO3 as produced above, onto the electrode surface, followed by necessary heat treatment to bulk diffuse calcium and chromium. This plasma spraying would give a high initial density before final heating. The impact of particles in the process of plasma spraying is not considered an appli-cation of pressure. Plasma spraying would only be used for oxide coated LaCrO3.
Additional application of a solid electrolyte layer over the remaining portion of the air cathode, if the electrolyte is to be applied after the interconnection, applying a cermet fuel electrode over the electrolyte, and then a cermet coating over the interconnection layer, will complete formation of an electrochemical cell, such as a fuel cell. Each fuel cell is preferably tubular and is electrlcally connected at least in series to an adjacent fuel cell. The electrical connection is made along the axial length of the interconnect through a metal fiber felt not shown in Figure 1. A typical cell generates an open circuit voltage of approximately one volt, and multiple cells can be connected in parallel in order to provide a de~ired system voltage.

In order to determine if calcium nitrate +
chromium nitrate would coat doped LaCrO3 powder, be converted to oxide form, and allow sintering of the doped LaCrO3 powder at temperatures below 1,600C, the following experiment was performed. In 25 ml. of water, 0.9214 g. of Cr(NO3)3 . 9H2O and 2.7371 g of CaNO3 .4H20 were dissolved in water. This would provide a wt. ratio of CaO:Cr203 of 3.714:1 upon heating to drive off H20 and then oxides of ~31~
14 54,174 nitrogen. Nineteen grams of LaO 83 SrO 16 CrO3, having a particle size distribution of from approximately 0.1 micron to 10 microns was mixed into the solution to form a slurry.
The slurry was dried at 100C to drive off H20.
The dried slurry was then pressed into a green pellet form.
As a control, untreated LaO.83 SrO.16 CrO3 p also formed into pellet form. Both types of pellets were heated at l,400C for 85 minutes without the application of pressure during the heating. The treated powder passed through the oxide formation stage and then through the melting range of CaO + Cr203 during the heating. It was calculated that the wt. ratio of CaO+Cr203 : LaO 83 SrO 16 CrO3 was approximately 0.0434:1. The density and open porosity of each composition as determined by the 5 Archimedes method is listed below in Table 1:

Density Open Porosity Sample g/cm3 ~
1. Control-untreated 4.39 32 .
20 2. Treated with Ca Nitrate + Cr Nitrate & heated L to form oxides of Ca+Cr 5.66 __ As can be seen, a very dense material resulted from the treated sample. Materials which were not found suitable as additives to the doped LaCrO3 powder included CeTiO3; CeO2+TiO2; LaF3+MgF2+CrO3; and LaF3+MgF2. The cerium material~ didn't help densification and the fluorine materials were very corrosive. Pressing in this Example was utilized only to provide a form for the material. In electrochemical cell application to an electrode, in one embodiment, the slurry itself would be coated directly onto an air electrode material and then heated and sintered without the application of pressure.

Claims (10)

1. A method of bonding a dense, electronically conductive layer on a porous, electronically conductive electrode structure comprising the steps:
(A) providing an electrode surface;
(B) forming, on a selected portion of the electrode surface, without the application of pressure, particles of LaCrO3 doped with an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the particles have a deposit on their surface comprising calcium oxide and chromium oxide;
(C) heating the particles with the oxide surface deposit in an oxidizing atmosphere at from 1,300°C to 1,550°C, without the application of pressure, to provide a dense, sintered, interconnection material bonded to the electrode, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO3.

2. The method of claim 1, where the weight ratio of calcium oxide:chromium oxide is from 0.4 to 9.0:1 and the weight ratio of calcium oxide and chromium oxide:doped LaCrO3 particles is from 0.005 to 0.10:1.

3. The method of claim 1, where the electrode is an air electrode, a solid electrolyte is applied to the uncovered portion of the air electrode, and a fuel elec-trode is applied to the solid electrolyte, to provide an electrochemical cell.

4. A method of bonding a dense, electronically conductive interconnection layer 26 on a porous, tubular, 54,174 electronically conductive air electrode structure 16 comprising the steps:
(A) providing an air electrode surface;
(B) depositing, on a selected portion of the air electrode surface, without the application of pressure, a mixture of:
(1) particles of LaCrO3 doped with an element selected from the group con-sisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, and (2) a salt solution comprising calcium and chromium, capable of forming oxides upon heating;
(C) heating the mixture up to 800°C so that the particles have a deposit on their surface comprising calcium oxide and chromium oxide;
(D) continuing heating the particles with the oxide surface deposit, in an oxidizing atmosphere up to from 1,300°C to 1,550°C, without the application of pres-sure, to provide a dense, sintered, interconnection materi-al bonded to the air electrode, where calcium and chromium from the surface deposit are incorporated into the struc-ture of the LaCrO3.

5. The method of claim 4, where the weight ratio of calcium oxide:chromium oxide is from 0.4 to 9.0:1 and the weight ratio of calcium oxide and chromium oxide:doped LaCrO3 particles is from 0.005 to 0.10:1.

6. The method of claim 4, where the doped LaCrO3 has the chemical formula La1-xMxCrO3, where M is a dopant element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, and x=0.075 to 0.25, and the air electrode is comprised of doped oxides or mixtures of oxides of the perovskite family.

7. The method of claim 4, where, in step (D), during continued heating the calcium oxide and chromium oxide initially melt at approximately 1,050°C to 1,250°C, completely coyer the doped LaCrO3 particles, and flow into 17 54,174 voids between the particles, and as the temperature is raised to from 1,300°C to 1,550°C, doped LaCrO3 near the melt dissolves into the melt and then solidifies after step (D) substantially filling the voids.

8. The method of claim 4, where the calcium oxide and chromium oxide are a mixture of CaO plus Cr2O3.

9. The method of claim 4, where the salt solu-tion deposited in step (B) is calcium nitrate plus chromium nitrate.

10. The method of claim 4, where a solid elec-trolyte is applied to the uncovered portion of the air electrode, and a fuel electrode is applied to the solid electrolyte, to provide an electrochemical cell.