METHOD FOR THE PREPARATION OF A SOLID OXIDE FUEL CELL SINGLE CELL AND THE NAMED CELL

FIELD OF THE INVENTION

This invention relates to high temperature fuel cell having mixed conducting cathode electrode, in particular solid oxide fuel cells and, more particularly, to solid oxide fuel cell cathode electrodes. More particularly yet, this invention relates to solid oxide fuel cell cathode electrodes with the enhanced specific surface area, nano (micro) mesoporous material pore volumes and a method for preparation of solid oxide fuel cell and nano (micro) mesoporous cathode electrode.

BACKGROUND OF THE INVENTION

Fuel cells are the modern electrochemical devices that convert the chemical energy of a fuel into electric energy and heat energy with high efficiency

[S. C. Singhal, Solid State Ionics 135, 305-313 (2000);

A. Weber, E. Ivers-Tiffee, J. Power Sources 127, 273-283

(2004); E. Lust, P. Mδller, I. Kivi, G. Nurk, S. Kallip,

P. Nigu, K. Lust, J. Electrochem. Soc. 152 (2005) A 2306; O. Yamamoto, Electrochim. Acta 45 (2000) 2423] . The basic structure of a fuel cell consists of the porous cathode

(oxygen reduction process) and porous anode (oxidation - fuel burning process) and a compact electrolyte layer between cathode and anode. In a typical fuel cell, fuels in a gaseous phase, typically hydrogen, methane etc are continuously fed to the anode electrode compartment and an oxidant typically oxygen from air (or pure oxygen) is

continuously fed to the cathode electrode compartment

[S. C. Singhal, Solid State Ionics 135, 305-313 (2000);

A. Weber, E. Ivers-Tiffee, J. Power Sources 127, 273-283

(2004); E. Lust, P. Mδller, I. Kivi, G. Nurk, S. Kallip, P. Nigu, K. Lust, J. Electrochem. Soc. 152 (2005) A 2306] .

The electrochemical oxidation and reduction reactions take place at or inside the porous structure of electrodes to produce an electric current and residual heat because the exothermic fuel oxidation reaction takes place as well as clean water vapour as a final chemical product forms.

In a solid oxide fuel cell the electrolyte is a nonporous compact mixed metal oxide, traditionally Y ₂ θ ₃ -stabilized ZrO ₂ (YSZ) for so-called high-temperature solid oxide fuel cells (working temperature T > 1073 K) and Sm ₂ O ₃ - stabilized CeO ₂ (CSO) or Gd ₂ O ₃ -stabilized CeO ₂ (CGO) , for the so-called intermediate temperature (773 < T < 973 K) solid oxide fuel cells. For high-temperature solid oxide fuel cells the cathode is typically Sr-doped LaMnO ₃ , but for intermediate-temperature solid oxide fuel cell the cathode is typically Sr-doped LaCoFeO ₃ or Sr-doped LaCoO ₃ , where the mixed conduction process of the oxygen ion occurs. The anode electrode is the metal (Ni or Cu) / YSZ cermet for the high-temperature solid oxide fuel cell

(973 < T < 1273 K) and Ni / CSO cermet for the intermediate temperature solid oxide fuel cell (773 < T < 973 K) [S. C. Singhal, Solid State Ionics 135, 305-313 (2000); A. Weber, E. Ivers-Tiffee, J. Power Sources 127, 273-283 (2004); E. Lust, P. Mδller, I. Kivi, G. Nurk, S. Kallip, P. Nigu, K. Lust, J. Electrochem. Soc. 152 (2005) A 2306; 0. Yamamoto, Electrochim. Acta 45 (2000) 2423] .

The most commonly used solid oxide fuel cell cathode material is mixed-conducting Laχ_ _x Sr _x MnO ₃ (Sr-doped LaMnO ₃ )

oxide, where x denotes the molar ratio of strontium added into LaMnO ₃ . However, the rate of electroreduction of oxygen from air is a very slow process and one possibility to increase the catalytic activity is to use the electrochemically more active Lai- _x Sr _x Coθ ₃ _ _δ or Lai- _x Sr _x Cθi_yFe _y θ ₃ - ₅ cathodes, where y is the molar ratio of Fe ³⁺ ions added into LaSrCoO ₃ [S. C. Singhal, Solid State Ionics 135, 305-313 (2000); A. Weber, E. Ivers-Tiffee, J. Power Sources 127, 273-283 (2004); E. Lust, P. Moller, I. Kivi, G. Nurk, S. Kallip, P. Nigu, K. Lust, J. Electrochem. Soc. 152 (2005) A 2306; O. Yamamoto, Electrochim. Acta 45 (2000) 2423; V. Dusastre, A. Kilner, Solid State Ionics 126, 163-174 (1999); A. Esquirol, N. P. Brandon, J. A. Kilner, M. Mogensen, J. Electrochem. Soc. 151, A1847-A1855 (2004)]. Another possibility is to increase the reaction volume (reaction area) through nano (micro)mesoporous structure of the cathode electrode layer. The nanopores are pores with width lower than two nanometers, named according to IUPAC classification as micropores.

SUMMARY OF THE INVENTION

There are disclosed a method for preparation of the solid oxide fuel cell single cell and a solid oxide fuel cell single cell with nano (micro) mesoporous cathode electrode working effectively from 723 to 1073 K.

The method for preparation of the solid oxide fuel cell single cell comprises the following steps:

(A) thermal decomposition of mixture of rare earth nitrate, strontium nitrate and cobalt nitrate to the mixed conducting corresponding rare earth

cobaltite activated with strontium ions (molar ratio of Sr ²⁺ from 0 to 0.6) in the presence of the reducing agent (e.g. glycine) and oxygen;

(B) preparation of the raw cathode paste by mixing rare earth cobaltite activated with strontium ions, mechanically uncompressible pore forming agent (e.g. carbon acetylene black powder with surface area 80 m ² g ^"1 in amount up to 30 weight percent of the total raw paste) , organic binder (e.g. ethylcellulose in amount up to 10 weight percent of the total raw paste) and solvent (e.g. turpentine oil) as nano (micro) mesopores forming agents for obtaining highly nano (micro) mesoporous cathode electrode;

(C) preparation of gadolinia and samaria doped ceria electrolyte at sintering temperature from 800 tolδOO K with the molar ratio of gadolinia or samaria in gadolinia or samaria activated ceria is varied from 0 to 0.20, before sintering pressed at pressure from 5 to 20 kN cm ^"2 during from 0.5 to 15 min;

(D) preparation of nano (micro) mesoporous cathode electrode and nano (micro) mesoporous cathode- electrolyte halfcell by burning out the pore forming agent, solvent and binder from the raw cathode electrode paste and sintering it onto the gadolinia or samaria doped ceria oxide oxygen ion conducting electrolyte at temperatures from 500 to 1673 K during 60-600 min;

(E) completing solid oxide fuel cell single cell by screenprinting Pt-paste onto the cathode-

electrolyte halfcell and sintering the fuel cell at temperatures from 800 to 1400 K during 6-600 iriin.

The molar ratio of rare earth element (e.g. lanthanum, praseodymium or gadolinium, etc.) in strontium activated rare earth cobaltite is varied from 1 to 0.4 in the A-site position of perovskite structure of rare earth cobaltite activated with strontium ions.

There is disclosed also a solid oxide fuel cell single cell working effectively from 723 to 1073 K which comprises highly nano (micro) mesoporous cathode electrode, anode electrode and electrolyte. The nano (micro) mesoporous cathode possesses very large surface area (10-500 m ² g ^"1 ) with the hierarchical nano (micro) mesoporous structure. The cathode is characterized by very high catalytic activity and thus having very low oxygen electroreduction activation energy varying from 0.3-0.8 eV at cathode electrode potential from -0.2 to 0 V versus porous PtIO ₂ reference electrode in air.

These and other subjects of this invention are addressed to a medium-temperature solid oxide fuel cell cathode comprising a micro nano (micro) mesoporous mixed conducting Lai- _x Sr _x CoC> ₃ , Pri- _x Sr _x CoC> ₃ , Gdi_ _x Sr _x Coθ ₃ structure produced by the thermal decomposition of the pore forming agents during initial cathode preparation cycle carried out at a temperature less than or equal to about 1500 K.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other subbjects and features of this invention will be better understood from the following description

taken in conjugation with the drawings given in Figures wherein:

PIGS 1, 2, 3 and 4 show the gas adsorption measurement data for nano (micro) mesoporous rare earth cobaltite powders, activated with strontium ions, based on Brunauer-

Emmett-Teller (BET) gas adsorption measurement method and calculated using density functional theory (DFT) (Figs 1 and 3) and Barret-Joyner-Hallenda model (Figs 2 and 4) explaining the pore size distribution, medium pore diameter, total pore volume and surface area, given in figures. The data in Figs 1 and 2 correspond to

Pr ₀ .6Sr ₀ .4CoO ₃ -S and in Figs 3 and 4 to Gdo.6Sr ₀ .4Coθ3-δ. The corresponding rare earth cobaltites activated with Sr ²⁺ ions have been prepared by the thermal decombination method from La (NO ₃ ) ₃ -6H ₂ O, Sr (NO ₃ ) ₂ and Co (NO ₃ ) ₃ -6H ₂ O and glycine mixture at temperatures from 373 to 1173 K;

FIGS 5 and 6 show the BET data for nano (micro) mesoporous

Lao.5Sr ₀ .4CoO ₃ -S cathode electrode sintered at Ceo.9Gdo.1O1.95 electrolyte at 1423 K during 5 hours;

FIGS 7, 8, 9, and 10 show the backscattered electron SEM

(scanning electron microscopy) images for nano (micro) mesoporous La ₀ .eSr ₀ . ₄ CoO ₃ - _S , Pr ₀ .6Sr ₀ .4CoO ₃ -S and

Gd ₀ .εSro. ₄ CoO ₃ - _S electrodes sintered at various temperatures from 973 to 1573 K and additions of carbon acetylene black powder from 0 0 10 wt% in raw cathode paste; figures 7 and 8 correspond to 1.36 weight %, figure 9 to 2.66 wt % and figure 10 to 5.24 wt % of carbon acetylene black powder addition into the unsintered raw cathode material;

FIGS 11 and 12 show the SEM data for the phase boundary region between Ceo. ₉ Gdo. ₁ O ₁ . ₉₅ electrolyte and nano (micro) mesoporous La _0-6 SrQ. ₄ CoO ₃ - _S cathode electrode

prepared by addition of 9.93 wt % carbon acetylene black powder into the raw cathode paste and burned out at 1427 K during 8 hours;

FIG 13 demonstrates the SEM data for electrolyte surface sintered at 1773 K during 8 hours;

FIGS 14, 15, 16 and 17 show the X-ray diffraction data for nano (micro) mesoporous cathode electrode (rare earth cobaltite activated with Sr ²⁺ ions) sintered at different chemical compositions: Figs 14 and 17 for Lao. ₆ Sro. ₄ Coθ ₃ - ₈ , Fig. 15 for Pr _0-6 Sr _0-4 CoO ₃ - _S and Fig. 16 for Gd ₀ . ₅ Sr ₀ .4CoO ₃ -S at T = 1423 K (Figs 14, 15 and 16) and at T = 1073 K (Fig. 17);

FIGS 18 and 19 show the ATM image and surface height profile of Lao. ₆ Sro.4CoO3.- ₈ cathode electrode structure sintered onto the Ceo. ₉ Gdo. ₁ O ₁ . ₉₅ electrolyte at temperature 1423 K;

FIGS 20, 21 and 22 show the cyclic voltammograms (current density vs. cathode potential plots) for nano (micro) mesoporous La ₀ .6Sr _0-4 CoO ₃ - _S cathode electrode | Ceo. ₉ Gdo. ₁ O ₁ . ₉₅ I porous Pt anode electrode single cell. Lao.βSro.4CoO ₃ - _S cathode electrode was prepared at sintering temperature T = 1423 K;

FIGS 23, 24, 25, 26, 27 and 28 show the complex impedance plane plots for nano (miro) mesoporous La ₀ . ₆ Sr _0-4 CoO ₃ - _S cathode electrode | Ceo. ₉ Gdo. ₁ O ₁ . ₉₅ | porous Pt anode electrode single cell at temperatures and cathode potentials, given in figures;

FIGS 29, 30, 31, 32 and 33 show the total polarization resistance vs. carbon acetylene black powder wt% plots

calculated from impedance plane plots for nano (micro) mesoporous La ₀ .6Sr ₀ .4CoO ₃ -S cathode electrode | Ceo.9Gdo.1O1.95 I porous Pt anode electrode single cell at different cathode electrode potentials and temperatures, noted in figures;

FIG 34 shows activation energy vs . cathode electrode potential plots for nano (micro) mesoporous La _0-6 Sr _0-4 CoO ₃ -B cathode electrode | Ceo. ₉ Gdo. ₁ O ₁ . ₉₅ | porous Pt anode electrode single cell, calculated from the impedance data in the case of various additions of carbon acetylene black powder into the raw cathode material, shown in figure.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention disclosed herein is a method for preparation of the solid oxide fuel cell single cell and a solid oxide fuel cell single cell with nano (micro) meso porous cathode electrode working effectively from 723 to 1073 K.

The invention works out the synthesis conditions of the nano-powder for Lai_ _x Sr _x Co0 ₃ _δλ Pri_ _x Sr _x Co0 ₃ -δ, and Gdi_ _x Sr _x Coθ3_δ cathode electrode with the nano (micro) size particles by the solution phase synthesis method from corresponding La (NO ₃ ) ₃ -6H ₂ O, Pr (NO ₃ ) ₃ -6H ₂ O, Gd (NO ₃ ) ₃ -6H ₂ O Sr(NOs) ₂ and Co(NOs) ₃ -GH ₂ O nitrates. The corresponding nitrates were dissolved in H ₂ O, where the known amount of a reducing agent glycine was added and dissolved before. Thereafter the mixture was heated to 353 K during from 0,5 to 3 hours to form a viscous solution of colloidal system. The hot solution was added drop wise to a Pt-beaker that was preheated between 573 and 673 K. Water was quickly evaporated from solution and the resulting viscous liquid swelled, auto-ignited and initiated a highly exothermic

self-continued combustion process, converting the precursor materials into the powder of the complex oxides. The evolution of gases during the combustion process helped in formation of fine ceramic nano (micro) powder containing some carbon residue. The powder was further calcined to convert to the desired product. Thereafter the powder was heat-treated in air at various temperatures between 700 and 1300 K during from 0.5 to 2 hours to form the crystalline phase with different crystallinities .

The received nano-powder of Lai- _x Sr _x Co0 ₃ _ _δ , Pri_ _x Sr _x Co0 ₃ _s, or Gdi- _x Sr _x Coθ ₃ -g was mixed with the pores forming agent (carbon acetylene black powder) with medium diameter from 100 nm to 10 μm. After adding the complex formation agent (ethylcellulose) and solvent (turpentine oil) the viscous raw cathode paste was prepared using mechanical rotator.

The received raw cathode paste has been screenprinted onto the said as prepared Gdi- _x Ce _x θ2-δ electrolyte tablet and thereafter sintered at fixed different temperatures from 800 to 1500 K during from 0.5 to 12 hours. The heating up temperature was usually 20 K min ^"1 .

After cooling down the ready for testing Gdi_ _x Ce _x θ2-δ electrolyte | nano (micro) mesoporous rare earth cobaltites activated with Sr ²⁺ cathode electrode was covered with Pt paste to guarantee good electrical conductivity between, as prepared by solution (nitrate) based method

Lai- _x Sr _x Co0 ₃ -δ, Pri- _x Sr _x Co0 ₃ -s or Gdi_ _x Sr _x CoO ₃ -δ cathode electrode surface and current collector (Pt mesh) .

The another i.e. free side of Gdi- _x Sr _x Co0 ₃ - _δ electrolyte was covered by Pt-paste, using screenprinting method and thereafter was sintered at temperature from 800 to 1473 K

to form the porous Pt-electrode with very large surface area. The cyclic voltammetry data (Figs 20-22), electrochemical impedance (Figs 23-28) and chronoamperometry methods were used for characterisation of oxygen reduction kinetics at nano (micro) mesoporous rare earth cobaltite activated with Sr ²⁺ ions cathode electrode prepared by method discussed before. The very high current densities (Figs 20-22) , and very low total polarization resistances (Figs 23-33) at working temperatures from 723 to 773 K show that the unexpectly highly effective cathode electrodes were prepared, characterized with surprisingly low activation energy values. The obtained cathodes are having very large surface area from 10-500 m ² g ^"1 , and characterised by very high catalytic activity and having very low oxygen electroreduction activation energy varying from 0.3-0.8 eV at -0.2...0 V cathode electrode potential versus porous Pt | O ₂ reference electrode in air.

These and other subjects of this invention are also addressed by a method of fabricating a medium temperature solid oxide fuel cell cathode electrode comprising the steps of forming a mixture of Lai- _x Sr _x Co03_s, Pri_ _x Sr _x Co0 ₃ _ _δ or Gdi-χSr _x Coθ ₃ - _δ particles and carbon acetylene black powder (pore forming agent) into a green or unsintered cathode structure typically with organic binders, heating the green cathode structure in air to a suitable sintering temperature, forming a sintered cathode electrode structure during heating at temperature from 700 to 1500 K and by the thermal decomposition of organic binders at temperature from 700 to 1600 K and following the oxidation of carbon acetylene black powder to CO ₂ in the temperature range from about 700 to about 1600 K forming a highly nano (micro) mesoporous cathode electrode catalytically

highly active and stable within the temperature range from 723 to 973 K.

The Brunauer-Emmett-Teller (BET) (N ₂ gas adsorption measurement at the nitrogen boiling temperature) analysis of nano (micro)mesoporous La _0-5 Sr _0-4 COO ₃ -S, Pr ₀ . ₆ Sr ₀ . ₄ Coθ ₃ -δ, and Gdo. ₆ Sr ₀ . ₄ Coθ ₃ - _δ cathode powders (Figs 1-6) shows that the materials with very large surface area (from 10 to 500 m ² g ^"1 ) can be synthesized by using the solution based nitrate decomposition method. The very narrow pore size distribution with medium pore diameter from 2.0 to 4.0 nm and very large total pore volume (given in Figs 1-6) have been obtained. Thus, in addition to the nano (micro) pores there are lots of mesopores inside nano (micro) mesoporous cathode powder (rare earth cobaltite activated with strontium ions) , characterised by the very good O ₂ molecules transport properties to the reaction zone or reaction volume (triple phase boundary area) . The data in figures 5 and 6 show that the nano (micro) mesoporous Lao. ₆ Sr ₀ . ₄ Coθ ₃ -g cathode electrode | Ceo.9Gdo.1O1.95 electrolyte halfcell has very narrow pore size distribution and large surface area (from 10 to 148 m ² g ^"1 ) .

Figs 7-10 show back scattered electron (BSE) scanning electron microscopy (SEM) images of nano (micro) mesoporous cathode electrode of the solid oxide fuel cell single cell after sintering and thermal decomposition of pore forming agents, binder and solvent at different amounts of pore forming agents, added to nano (micro) particle Lao.6Sr ₀ .4Coθ ₃ _ _δ powder. As can be seen from these figures (Figs 7-10) the very nice porous microstructure of the cathode has been formed. The SEM data in Figs 7-10 show that the very mesoporous Lao.6Sro. ₄ Coθ ₃ - _δ cathode electrode were performed and the mesoporosity depends strongly on the amount of

pore forming agent in the raw cathode material prepared as discussed in previous chapter. The data in Figs 7 and 8 correspond to 1.36 wt%, Fig. 9 to 2.66 wt% and Fig. 10 to 5.24 wt% carbon acetylene black powder addition into the raw cathode paste.

Figs 11 and 12 show the nano (micro) mesoporous cathode electrode | Ceo. ₉ Gdo. ₁ O ₁ . ₉₅ electrolyte interface, and it is very well visible that cathode is mesoporous and the SEM data in Figs 11, 12 and 13 show that there is no pores inside the Ceo. ₉ Gdo. ₁ O ₁ . ₉₅ electrolyte prepared from Ceo. ₉ Gdo. ₁ O ₁ . ₉₅ nanopowder and sintered at T = 1773 K during 300 min. As obtained herein, the amount of carbon acetylene black powder has very high effect on the sintered Lao. ₆ Sro. ₄ Coθ ₃ - _δ nano (micro) mesoporous structure.

The X-ray diffraction data (Figs 14, 15, 16 and 17) for the nano (micro) mesoporous cathode electrode (rare earth cobaltite activated with Sr ²⁺ ions) as prepared sintered onto gadolinia stabilized ceria electrolyte at T = 1427 K, show a good crystallinity according to the trigonal R-3c perovskite-type structure for Lao, ₆ Sro. ₄ Coθ ₃ _g (Fig. 14),

Pro.6Sr ₀ .4Co0 ₃ -δ (Fig. 15) and Gd ₀ .6Sr ₀ .4CoO ₃ -S (Fig. 16) in the case of sintering temperatures from 1173 to 1473 K during 5 hours at least. For Lao. ₆ Sr _0-4 CoO ₃ - _S (Fig. 17), Pro.βSro.4CoO ₃ - _S and Gd ₀ .6SrO _-4 CoO ₃ - _S cathode electrodes as prepared, sintered at temperature lower than 1073 K during from two to five hours, the crystallinity is not so good as for La ₀ . ₆ Sr _0-4 CoO ₃ - _S , sintered at T > 1173 K during five hours. The cyclic voltammetry data (Figs 20-22) and impedance data (Figs 23-28) show that only the nano (micro) mesoporous cathode electrodes having good crystallinity can be used the nano (micro) mesoporous cathode electrode | Ceo. ₉ Gdo. ₁ O1. ₉₅ | porous Pt anode single

cells, characterised by low oxygen electroreduction activation energy (Fig. 34).

The atomic force microscopy (AFM) data given in Figs 18 and 19 show that the very rough cathode surface has been formed and the bigger microscopic crystallites from 2 to 5 μm consist of the nano (micro) particles from 2 to 10 nm. The sintering temperature has very high effect on the nano (micro) mesoscopic structure of nano (micro) mesoporous Lao. ₆ Sr ₀ . ₄ Coθ ₃ - ₅ cathode electrode for the intermediate temperature solid oxide fuel cell, and at sintering temperature T <1173 K the very amorphous cathode electrode structure has formed.

Surprisingly, the cyclic voltammetry curves (Figs 20-22) for the nano (micro) mesoporous Lao. ₆ Sro.4CoC> ₃ _δ cathode electrode | Ceo. ₉ Gdo. ₁ O ₁ . ₉₅ electrolyte | porous Pt anode single cell show that the very high current density

(catalytiv activity) has been obtained for the nano (micro) mesoporous Lao. ₆ Sro. ₄ CoO ₃ .-s cathode electrode, where the carbon acetylene black powder (pore forming agent) in the raw cathode material was from 2.56 to 1.36 wt%. The nano (micro) mesoporous cathode electrodes prepared from raw cathode paste where the wt% of the carbon acetylene black powder was higher than 2.56 or lower than 1.36 wt% did not give so high O ₂ electroreduction current densities.

The normalized complex impedance plane plots in Figs 23-

28, where Z' is an active real part of complex resistance and Z' ' is a so-called capacitive resistance (imaginary part of complex resistance) , show that the total polarization resistance R _p , obtained as a real impedance

(resistance) value at alternative current frequency Jf =0,

surprisingly strongly depends on the amount of pore forming agent (carbon acetylene black powder) in the raw cathode paste, burned out at sintering temperature from 500 to 1573 K. The very low R _p values (Figs 29-33) have been obtained at working temperature T = 973 K for La ₀ . _δ Sr ₀ . ₄ CoO ₃ - _S cathode electrode potential at -0.2 V versus porous Pt I O2 reference electrode.

The amount of electrochemical performance of solid oxide fuel cell cathode electrode, expressed as the total polarisation resistance R _p (Figs 29-33) obtained from the impedance spectroscopy analysis (Figs 23-28) shows that, in the as prepared, i.e. sintered Lao.eSro. ₄ CoO ₃ - _S cathode electrode activity is maximal {R _p is minimal) for cathodes with intermediate carbon acetylene black powder addition from 1.36 to 2.56 wt% of carbon acetylene black powder in raw cathode material. The very low total polarization resistance values for the as prepared cathode electrode show the very high catalytic activity of the nano (micro) mesoporous Lao. ₆ Sr ₀ .4Coθ3-δ cathode electrode at T > 773 K.

The data in Fig. 34 show that the Arrhenius activation energy E _act , calculated for oxygen electroreduction process for nano (micro) mesoporous La ₀ .6Sr ₀ . ₄ Co0 ₃ _s cathode electrodes | Ceo. ₉ Gdo. ₁ O ₁ . ₉₅ electrolyte | porous Pt anode single cell, prepared using methods discussed before, has minimal values for nano (micro) mesoporous cathode electrode with the amount of pore forming agent said carbon acetylene black powder from 0.5 to 2.5 wt%. The values of ■E _act decrease with increasing the cathode electropolarisation of the cathode (i.e. cathode electrode potential) in agreement with the data in Figs 20-33 for

nano (micro) mesoporous cathodes, prepared according to the preparation and sintering method discussed before.

It is believed that the methods and examples shown or described above have been characterized as preferred, various changes and modifications may be made therein without departing from the scope of the invention as defined in the following claims.

Although the invention is described herein in the context of medium temperature solid oxide fuel cells and cathode electrodes sintered at gadolinia doped ceria electrolyte thereof, it will be appreciated by those skilled in the art that the basic principles of this invention may be advantageously applied to other high-temperature fuel cells employing the mixed conducting cathode electrodes to produce highly nano (micro) mesoporous cathode electrode materials at oxygen ion conducting electrolytes.