RU2125324C1 - Method for producing single high-temperature fuel element and its components: cathode, electrolyte, anode, current duct, interface and insulating layers - Google Patents

Abstract

FIELD: chemical-to-electrical energy conversion; high-temperature electrochemical devices with solid oxide electrolyte for mobile and stationary high-power plants. SUBSTANCE: method involves use of narrow range of fossil chemical agents whose production in large quantities (thousands of tons) has been already harnessed. As a consequence, procedure is conducted in the framework of single physical and chemical process using single-type process equipment. EFFECT: reduced power requirement and quantity of materials for process equipment; reduced cost of finished product. 55 cl, 11 dwg, 5 tbl, 15 ex

Description

 The proposed group of inventions relates to the field of direct direct conversion of chemical energy of fuel into electrical energy, and in particular, to high-temperature electrochemical devices (VTEHU) with solid oxide electrolyte (TOE) and can be used to produce a single high-temperature fuel cell (VTTE) and its components.

 Today, high-temperature fuel cells are one of the promising sources of electric energy, both in mobile units and in stationary power plants of high power, and can be considered as an alternative to nuclear energy.

 The most important feature of VTE is the direct conversion of the chemical energy of certain types of fuel into electrical energy, due to which such energy conversion does not fall under the limitations of the Carnot cycle and theoretically it is possible to achieve an efficiency of 80%. At present, the efficiency values of 50% have been achieved with the prototypes, and the efficiency values that are actually achievable in the near future will be 65 - 70%. In addition, compared with traditional methods of generating electricity, fuel cells have a number of other advantages: modular design, high efficiency at partial electric load, the possibility of joint generation of electric and thermal energy, the output of polluting products is several orders of magnitude lower, the absence of moving parts and assemblies.

 Recently, the most active research and development of high-temperature solid oxide fuel cells (according to the international classification "Solid Oxide Fuel Cells" (SOFC).

They have several distinct advantages over other types of fuel cells, such as: the use of oxide materials for electrodes, the absence of liquids in the fuel cell, their circulation, i.e. advantage of solid electrolyte. The use of solid oxide electrolyte in a ceramic fuel cell eliminates the corrosion of materials and the task of monitoring the electrolyte. Ceramic fuel cells typically operate at high temperatures (> 600 ^° C). High operating temperatures increase the reaction rate, allow the conversion of hydrocarbon fuel in a fuel cell (internal reforming) and produce high-potential heat suitable for regeneration and use in the main cycle. Thus, power plants based on ceramic fuel cells can be simpler and more efficient than many other known technologies for generating electric and thermal energy. Moreover, since all the components of the solid fuel cell are in the solid state, ceramic fuel cells can be formed in the form of very thin layers, and the components of the element can be given unique shapes, which is unattainable in fuel cell systems using liquid electrolyte.

 On the other hand, ceramic fuel cells place increased demands on the materials used to make their components. The preparation of ceramic powders and the development of methods for their formation and production play a key role in ceramic fuel cell technologies.

 The main components of a ceramic fuel cell are an electrolyte, an anode, a cathode, and a current passage. Each component performs several functions in the fuel cell and must meet certain requirements: to have stability of properties (chemical, phase, structural, dimensional) in oxidizing and / or reducing environments, chemical compatibility with other components and proper conductivity. Components of ceramic fuel cells should have similar thermal expansion coefficients to prevent delamination and destruction during manufacturing and operation. The electrolyte and current passage must be sufficiently dense to prevent mixing of the gases of the anode and cathode spaces, while the anode and cathode must be porous in order to ensure gas transfer to the reaction site and removal of reaction products.

 In addition to the listed requirements, the cell components must have high strength and durability and provide the possibility of a simple and cheap method of its manufacture. In addition, the methods for manufacturing ceramic fuel cell components must be compatible, since the production conditions of the cell cannot be separated and independent for each component. For example, if the components are made and combined one after another, then the sintering temperature of each subsequent component should be equal to or lower than for the previous component in order to avoid changes in the microstructure of the previous one. If the components are formed in raw form, then all of them must be sintered in the same modes. Moreover, the components of a ceramic fuel cell must be compatible not only at operating temperature, but also at higher temperatures at which ceramic structures are formed.

Currently, manufacturing technologies (VTTE) have been developed and are widely used, their components: electrodes, electrolytes, current paths, which basically satisfy the requirements for chemical stability, heat resistance, electrical and other properties. Their compositions are mainly ceramic materials based on zirconia, ceria, thorium, barium, strontium, bismuth and perovskite-type compounds based on chromium, manganese, cobalt, nickel, lanthanum oxides, modified with magnesium, calcium, strontium, barium, scandium, yttrium, cerium and other lanthanides. In the technology for manufacturing materials for VTTE, all known methods for the manufacture of ceramic materials are applicable. However, the increasing and increasing specific requirements for the design of VTTE as a whole, such as:
- predetermined porosity of ceramic electrodes with sufficient structural strength and electrical conductivity;
- a decrease in the thickness of the electrolyte film while maintaining gas density and, as a consequence, the need to form thin electrolyte films on porous supporting electrodes with a maximum increase in the specific working surface per unit weight of VTTE, significantly limit the use of known ceramic technologies and materials in the formation of the components of VTTE - electrodes, electrolytes current passages, etc.

One of the limitations is due to large differences in the sintering temperatures of the materials from which the mated VTTE components are made (for example, sintering of 10YSZ electrolyte occurs at a temperature of 1700 ^o С, and of a bearing cathode of manganite-lanthanum-strontium La _0.7 Sr _0.3 MnO ₃ - at 1450 ^o C). At the same time, these temperatures, characteristic of each material, are necessary for the complete stabilization of their properties used in VTE. Therefore, special methods developed in recent years for the formation of solid oxide electrolytes and electrodes are ineffective, because they are mainly based on the maximum increase in the activity of powders to reduce and approximate sintering temperatures of electrolytes and electrodes. Indeed, it is possible to form the contact surfaces of VTTE: cathode / electrolyte / anode at temperatures 100-400 ^o C lower than usual. However, the materials, already being part of the product and continuing to remain quite active, continue to acquire a phase structure already during operation of the product at 900 - 1100 ^o C, which is accompanied by uneven shrinkage of various components of VTTE, their increased mutual diffusion, leading to destruction or unacceptable decrease in operational product properties.

 In modifications of the well-known ceramic technologies, in which the methods for the formation of HTFC components from powders (isostatic pressing, extrusion, plasma spraying, vacuum spraying, etc.) are changed, they are forced to use active powders either during the formation itself or further through the manufacturing process using additional techniques: compaction of the electrolyte, providing a given porosity or increasing adhesion of the mating elements, etc.

A known method of manufacturing VTFC, including the sequential deposition of a fuel electrode layer, an electrolyte layer and an air electrode layer forming a three-layer element on a carrier substrate made of CSZ, and the electrolyte layer is made of YSZ, wherein the substrate is made with a CTE equal to the CTE of the electrolyte layer deposited by spraying with heat treatment during application. Heat treatment is carried out by heating at a speed of 50 ^o C / hour to reach a temperature of 1450 ^o C, keeping at this temperature for 6 hours, followed by a decrease at the same speed (US patent N 5021304, CL H 01 M 8/10, H 01 M 4/86, publ. 1991).

 In the manufacture of VTTE in accordance with this patent, a wide range of starting materials and compounds is used. The manufacture of its individual components: cathode, anode, electrolyte, current passage, interface and electrical insulating layers is carried out by various technologies, which ultimately complicates the manufacturing process of the entire VTFC as a whole and especially complicates its hardware implementation.

 An alternative to this method can be technologies using processes based on the pyrolysis of metal compounds with various organic reagents containing elements that are part of the formed components of VTTE.

 An analysis of known similar technical solutions allows us to conclude that the role of organic reagents in the manufacture of electrolytes and electrodes is the same in terms of lowering sintering (formation) temperatures, but it is different, namely, the opposite - in terms of the desired final result, because electrolyte must be gas tight and the electrode porous. In this case, there is a tendency to use different classes of organic compounds, which ultimately leads to the inevitable expansion of the used range of substances and materials and the cost of manufacturing VTTE as a whole.

 So, while β-diketones are mainly used in the methods of electrolyte formation, then in the methods of electrode formation there are other, very different, classes of organic compounds: alcohols, carboxylic acids, amines, and many others (including flammable ones), for various metals and metal groups.

 In this regard, the process of manufacturing materials for the formation of any components of VTTE should be universal and fit into the framework of the same processes and equipment, both in the manufacture of the materials themselves and components of VTTE on their basis, which significantly reduces the cost of the product, reduces the range of materials and substances used, as well as all used technological equipment.

The ceramic cathode can be the supporting structural basis of VTTE. The following basic requirements are imposed on the fuel cell cathode:
- the total porosity and pore size of the cathode should provide a free supply of oxygen-containing gas to the three-phase interface "cathode-electrolyte-gas";
- sufficient mechanical strength to ensure reliable operation of the fuel cell for a long time;
- the coefficient of thermal expansion (CTE) of the cathode should be close to the CTE of the solid electrolyte, to exclude the occurrence of mechanical stresses leading to the destruction of the solid electrolyte layer.

 The first two requirements contradict each other, so in practice there is always the problem of finding their compromise value.

 The third requirement is mainly provided by the choice of materials.

 As the material for the manufacture of the cathode, for example, oxide compounds La, Mn, Cr, Co, Ni, doped with oxides of Mg, Ca, Sr, Ba, etc. are used.

Given the requirements, including due to high operating temperatures (about 1000 ^o C), noble metals or oxide compounds with electronic conductivity can be used in the YSZ-based SOFC to produce cathodes. However, noble metals such as platinum, palladium or silver, due to their high cost, are practically used in SOFC for research purposes only. Recently, doped lanthanum manganite LaMnO ₃ has become most widespread.

 As noted above, the choice of material for the manufacture of a supporting porous cathode is carried out taking into account its conductivity, KTP, and other properties. In this regard, the temperature of preliminary firing (synthesis) of the selected material is a predetermined (due to the temperature at which the material acquires the necessary phase composition) and cannot be changed over a wide range. This, in turn, does not allow to vary the diffusion and strength characteristics of the supporting porous cathode. In addition, sintering at high temperatures involves large energy costs for the production of fuel cells.

 It is known from the prior art that methods for manufacturing electrodes differ depending on the design of the VTFC.

 In constructions with a supporting electrolyte, the manufacture of electrodes (in most cases) consists in applying a suspension of finely dispersed material in any solvents (alcohol, acetone, etc.) to the surface of the electrolyte, followed by firing at a temperature that ensures reliable adhesion of the electrode material with the electrolyte . The application of the electrode mass on the surface of the electrolyte is usually carried out by painting, dipping or spraying.

 The electrode can also be made by chemical deposition on the surface of a supporting solid electrolyte from solutions or the gas phase, thermal decomposition of metal salts, joint hot pressing of the electrode material with electrolyte, sputtering (Perfilyev M.V., Demin A.K., Kuzin B.L., Lipilin, A.S., High-Temperature Electrolysis of Gases, Moscow: Nauka, 1988, p. 98).

 In designs with a supporting electrode, the electrodes are made by various molding methods: extrusion, uniaxial or isostatic pressing, casting, from specially prepared molded masses.

Closest to the claimed group of inventions in relation to the manufacture of the cathode in technical essence and the achieved result is a method of manufacturing a tubular support electrode for a solid oxide electrolyte of an electrochemical cell, which consists in dry mixing powders of MnO ₂ , CaCO ₃ and La ₂ O ₃ (to obtain manganite after sintering lanthanum (LaMnO ₃₎ doped with calcium), pressing the resulting mixture into briquettes, high-temperature synthesis by sintering the compacted briquettes and subsequently grinding them down to the floor powder with a given particle size, mixing the prepared powder with removable: plasticizer, blowing agent and a water-soluble binder to obtain a moldable mass, its molding into thin-walled tubes and their subsequent sintering (US patent, N 5108850, CL H 01 M 4/88, publ. .1992).

 In addition to the limitations inherent in known similar technical solutions, the solid-phase synthesis used in the technology protected by this patent does not provide homogeneous powder properties. In addition, it provides for the use of a plasticizer, a blowing agent and a water-soluble binder. The sintering process occurs at high temperatures with large shrinkage, which requires additional techniques to obtain the product of the required size, i.e. the technology is quite labor intensive and energy intensive.

High-temperature solid oxide electrolytes fuel cells currently under development can be divided into two classes: those that conduct on oxygen ions and on hydrogen (proton) ions. Among the many investigated high-temperature solid electrolytes, two types are considered promising in terms of physicochemical properties and chemical composition:
- an electrolyte with ionic oxygen conductivity based on modified zirconia;
- an electrolyte with ionic proton conductivity based on modified barium cerate (or strontium cerate).

 Currently, many companies are working on projects for the manufacture of (1 - 10) kW generators: Westenghouse Electric Corp. (USA), Fuji Electric Co. (Japan), Asea Brown Boveri AG (Germany), NGK Insulators Ltd (Japan), Mitsubishi (Japan), Osaka Gas Co. (Japan), Allied-Signal Inc. (USA), Siemens AG. (Germany), International Fuel Cell Corp. (USA) and others.

 Such attention to the problem is due to those potential physicochemical properties that are embedded in solid electrolytes and, accordingly, can be implemented in electrochemical devices.

It is likely that by 2000 generators (0.5 - 1.0) MW with specific power (1.0 - 1.5) W / cm ² will be manufactured.

Currently, the closest to industrial implementation by the degree of development is VTTE based on zirconia in a tubular design. Research and practical work on VTE with modified barium cerate (strontium) is being carried out in connection with the exceptional potential of proton electrolyte. This is confirmed by an analysis of the known state of technology, including scientific works on proton electrolyte, its wide discussion at international scientific seminars and conferences. On some samples of thin-film (σ = 10 - 15 μm) proton electrolytes, a current density of 0.3 A / cm ^{3 was} achieved at a voltage of 0.4 V and a temperature of 600 ^o C. These values are approximately three times higher than with an electrolyte based on zirconium dioxide under the same conditions, due to the very low polarizability of traditional electrodes in contact with this ceramic and lower activation energy than that of a zirconium electrolyte at temperatures below 800 ^o C.

However, it should be noted that the realization of the above-mentioned advantages of electrochemical devices at a high level is possible only when solving a common problem for all areas - the development of the latest technologies both in the production of the necessary ceramic materials and in the use of these materials in the manufacturing process of VTEs themselves. The task of creating a technology for applying gas-tight layers (σ = 1 - 40 μm) of electrolytes on supporting electrodes (gas-tight and porous) is especially time-consuming. For proton electrolyte designs, the thin-film design is of particular importance, since in this case the ohmic is the main loss, and the BaCeO ₃ electrolyte ceramic has a significantly lower mechanical strength compared to ZrO ₂ and, therefore, cannot simultaneously fulfill two functions of the structural support material cell and electrolyte.

 Scientific and technical problems in the manufacture of thin-film electrolytes are complemented by the high cost of their manufacturing technology. So, even if all technical problems are solved, but the technology will include maintaining parameters to obtain reproducible characteristics, for example, temperature, with an accuracy of 2 degrees, this is an unacceptably expensive and unreliable technology.

 At the same time, the well-known two-stage high-temperature synthesis of oxide powder materials for the manufacture of thin-film electrolytes is unacceptable today, since ultrafine powders that are extremely uniform in chemical composition or technology of forming electrolyte layers without an intermediate stage of powder production are required to form layers with a thickness of 1 - 40 μm.

Known methods in which there are no stages of manufacture and sintering of powders of solid electrolytes. For example, in the EVD technology used by Westinghouse, the synthesis of a dense electrolyte on the porous surface of the supporting cathode is carried out from gaseous reagents decomposed at the cathode, while gaseous zirconium and yttrium halides are used as the starting material for the synthesis. The advantage of this method is that the formation of a layer can occur from scratch with the participation of free particles of the molecular level from the gas phase. This largely solves the problems of gas tightness. However, the need to use unique equipment and the need to work with aggressive gas environments of halide compounds makes this technology unprofitable (US patent N 5085742, class H 01 M 6/00; H 01 M 8/00, publ. 1992). In addition, a drawback of the CVD (EVD) method is the natural disproportionation of the gas phase mixture of zirconium tetrachloride and yttrium trichloride during their deposition on the substrate. As a result of this, the distribution of yttrium in the applied electrolyte is uneven and has a concentration gradient from the boundary with the substrate to the surface. At the same time, in addition to cubic zirconia, its monoclinic phase appears, which does not allow the manufacture of a gas-tight electrolyte layer with properties that are stable during operation. There is also known a method of manufacturing components, which uses organic compounds of the elements that make up the electrolyte (Zr, Y, etc.), the cathode (La, Mn, Sr, etc.), current passage, anode, etc., which are easily dissociated by heating, which allows the formation of HTFC components at relatively low temperatures <600 ^o C, in inert environments or oxygen atmosphere of air at atmospheric pressure without intermediate stages of deposition of a porous layer of electrolyte, for example by plasma spraying.

 From the analysis of publications and patent literature it follows that the method of applying metal oxides from their organic compounds, previously used only for the preparation of protective coatings on structural materials (Kuntagai Tozhija, Johota Hvozhi, Shindon Juji, Kondo Wakicki, Mizuta Suzumu, Dyanki Naganu, Koge Butsuri Kaganu ; Anform Water. Energy Theory Life, 1987, 55, N 3, p. 269 - 270. Preparation of perovskite-type thin oxide films by pyrolysis of salts of organic acids (Perfiliev MV, Demin AK, Kuzin B. L., Lipilin, A.S., High-Temperature Electrolysis of Gases, Moscow: Nauka, 1988, pp. 66–70, Velikobr patent Taniya N 136198, class C 1 A, 1974, Japanese application N 62-235475, 1987, IPC C 23 C 20/08, C 03 C 17/25) is currently being actively developed for solid oxide electrolytes and electrodes (Sat Scientific works edited by Academician Spitsin V.I. Structure, properties and application of metal β-diketonates. - M .: Nauka, 1978, p. 116 - 119; Katrin Nord-Varhaug, Chun - hua Chen, Frik M. Kelder, Frans pe van Berkil and Joop Schoonman, "Thin Film Techniqnes for Solid Electrolyte Composites". European solid oxide fuel cell forum. 6-10 May 1996. Oslo / Norway. Pg 331-340; European patent N 0478185 B1, IPC6 H 01 M 8/12, H 01 M 4/86, publ. 1991).

In the technology for the manufacture of electrolytes, the formation of oxide film coatings during the thermal decomposition of acetylacetonates Zr, Ce, etc. is essential. In this case, the formation of oxide compounds of a cubic structure due to carbon stabilization is noted. The cubic structure of zirconia stabilized by carbon is stable in air up to 900 ^o C. Above this temperature, due to the partial oxidation of carbon in air to CO and CO ₂ , the cubic form transitions to monoclinic. The authors, under the conditions of derivatographic analysis, succeeded in using the combined decomposition of β-diketonates (with pivaloyl trifluoroacetonate) zirconium and cerium to obtain fully stabilized zirconia (CSZ).

Closest to the present group of inventions in relation to the method of manufacturing an electrolyte according to the technical essence and the achieved result when used is a method of manufacturing a film electrolyte Zr / Y by electrostatic deposition of β-diketonates from a gas-droplet emulsion (ESD) medium. The process is carried out using zirconium and yttrium acetylacetonates (Zr (O ₂ C ₅ H ₇ ) ₄ , Alfa / Y (O ₂ C ₅ H ₇ ) ₃ Alfa). The essence of the method lies in the fact that in a closed chamber volume a gas-drop emulsion of a mixture of β-diketonates is sprayed. The substrate placed in the chamber is electrostatically charged up to 8-10 kV, heated from 250 to 430 ^o C. As a result, the emulsion droplets fall on the substrate and thermally decompose, forming a YSZ film on the surface.

When applying the ESD method, it is necessary to use metal chelates, namely acetyl acetonates, which have a high melting point of 194 ^° C, as a result of which acetylacetonates must be dissolved in ethanol, butyl carbitol and other solvents, which does not allow the use of a concentration of zirconium dioxide in solution of more than 0 , 05 mol / dm ³ . Such a low concentration limits the film deposition rate to 2 μm / h. In addition, since chelate ligands are strongly bonded to a metal atom, the decomposition of zirconium acetylacetonate occurs through the formation of an intermediate product of a polymer structure, which is destroyed not with the release of whole chelate ligands, but with the destruction of themselves, the carbon chain residues of which compete in the crystal lattice of zirconium dioxide with yttrium oxide. Thus, the zirconium dioxide, in addition to Y ₂ O ₃ , is partially stabilized by carbon chain residues, which, upon further firing, are released from the crystal lattice of zirconium dioxide in the form of CO and CO ₂ , as a result of which a certain amount of monoclinic structure is formed (3 - 4%) with the inevitable formation of pores.

 As noted above, the current passage is also one of the main components of VTTE. Among the list of requirements for the properties that the current passage used in VTTE should satisfy, the main thing is high electrical conductivity in both reducing and oxidizing atmospheres. Such property can provide current passages made of noble metals or alloys based on them.

 A known design of a high-temperature fuel cell, in which the current passage is made of an alloy of precious metals (US patent N 3457052, CL B 21 B, B 21 C, publ. 1969). Given the high cost of these materials, the manufacture of current paths from them on a large scale is almost impossible.

Current paths made of electrically conductive materials based on metal oxides and their compositions are more promising. These include doped lanthanum chromite (LaCrO ₃ ), since it is sufficiently stable both in the oxidizing atmosphere of the oxygen space and in the reducing atmosphere of fuel gas.

One of the requirements for the LaCrO ₃ current passage material used in SOFC is its gas density to avoid cross-leakage of fuel or oxidizing gases through it. It is known that LaCrO _{3 is} difficult to manufacture with high density under conditions of high oxygen activity. In this case, temperatures above 1600 ^o C. are necessary. Such high sintering temperatures become unacceptable when LaCrO _{3 is} sintered together with other SOFC components. The introduction of low-melting substances that improve sintering in the form of a second phase with a significantly lower melting point (~ 1400 ^o C), contributes to the compaction of LaCrO ₃ in oxidizing environments. However, such a method of lowering the sintering temperature is also unacceptable, since the departure of the liquid phase of the low-melting eutectic to other components of the fuel cell causes material and morphological changes that lead to the loss of the functional properties of the fuel cell.

 Closest to this group of inventions with respect to the manufacture of a current passage by technical nature and the achieved result when used is a method of manufacturing a current passage, comprising synthesizing a powder of an electrically conductive material based on doped lanthanum chromite and subsequent thermal spraying of a switching layer from this material onto an unmasked sector of an air electrode (US patent N 5085742, CL H 01 M 6/00, H 01 M 8/00, publ. 1992).

 The current passage made using this technology has lost a number of drawbacks inherent in the known technical solutions mentioned above. At the same time, for the production of a sufficiently gas-tight current passage from lanthanum chromite by this method, complex technological equipment is required, leading to a significant increase in the cost of the entire product.

 On the interface surfaces of high-temperature electrochemical devices, basic physical and chemical processes occur that ensure the operation of the device as a whole.

 The chemical composition of the layers of a single VTTE: a positive electrode / electrolyte / negative electrode (PEO), as a rule, is selected by the maximum electrical conductivity (electronic, ionic). In general, this choice rarely coincides with other functionally necessary requirements for materials: chemical and thermal resistance, structural strength, etc.

Chemical interfaces are possible on the interface between the electrodes and the electrolyte under operating temperature conditions or during the manufacturing process. So, at the LSM / YSZ interface, the formation of La ₂ Zr ₂ O ₇ lanthate zirconate occurs, which leads to a sharp increase in contact resistance and a deterioration in the cathode performance (Andreas Mitterdorfer et al. ETH Zurich, “Materials Department, Swiss Institute of Technology”, Second ESOFC Forum Oslo ( Norway), May 1996. Pp373 - 382).

 It is promising to use a modified cerium oxide having an ionic conductivity higher than that of a modified zirconium dioxide as an electrolyte. However, in the reducing atmosphere of the fuel, cerium oxide has a noticeable electronic conductivity, which can lead to a 20–30% decrease in the emf (open circuit voltage of the PEO) (M. Sahibzada et al. Departament of materials and departament of chemical engeneering technology, Imperial coolege of science , technology and medicine, London, Second ESOFC Forum Oslo (Norway), May 1996. Pp687 - 696).

Doped strontium lanthanum manganite is today one of the promising materials for the air electrode. However, since it is easily restored with a sharp increase in the KTP from 12.5 • 10 ^-6 to 14.5 • 10 ^-6 K ^-1 even in a weakly reducing atmosphere, its use is possible only with absolutely dense layers of solid electrolyte. Any local leakage of the electrolyte in contact with MLS quickly leads to the destruction of the entire cell. And since at present the tendency to decrease the thickness of electrolytes (in the future to 5 μm and below) prevails, the probability of the existence of point microdefects is very high.

 In order to solve the problems of efficient operation of mating materials in VTE, as well as increasing the stability of materials in working gas media, it is necessary to form special intermediate layers on the interface, which are called interface layers. As a rule, the thickness of the interface layers does not exceed units of micrometers.

 The creation of such thin interface layers makes special demands on the technology of their formation. Until 1994, two processes could be considered the most acceptable: - electrochemical deposition from the vapor-gas phase (EHF) and magnetron sputtering (which came from the technology of growing epitaxial layers in the manufacture of microcircuits). Both technologies in the production of VTEHG are not economically viable, since their practical implementation requires expensive equipment, as well as high operating costs.

 Of the cheaper technological processes, the pyrolysis decomposition of organometallic complexes, organometallic compounds, or mixtures thereof is promising. Its variety is electrostatic pyrolysis deposition (EPN), which is the closest to this group of inventions in terms of the manufacture of the interface layer.

 The second electrode of VTTE is the anode, usually made of cermet.

 Based on the above requirements for the electrodes and due to both their manufacturing technology and operating conditions, it can be stated that the most significant of them is the choice of material used to make the anode. The following circumstances are taken into account.

Due to the presence of reducing conditions in the atmosphere of fuel gas, metals are used as the anode material for SOFC. Since the composition of the material can change during the operation of the fuel cell, the metals used should not be oxidized not only in clean fuel, but also in conditions of the greatest oxidation of the fuel at the exit of the fuel device. At operating temperatures of 700 - 1000 ^o C in SOFC with solid electrolyte, the list of materials used is limited mainly to nickel, cobalt and noble metals. Nickel is most common due to its low cost (compared to cobalt, platinum, etc.). To obtain a cermet anode with a porous structure, operating for a long time at 700 - 1000 ^o C and provide other necessary properties, nickel in the form of a metal is usually used with stabilized zirconia, as well as with stabilized cerium oxide, which is necessary for additional (internal) fuel gas reforming. The base of ion-conducting ceramic material holds particles of metallic nickel, prevents sintering of metal particles at operating temperatures of the fuel cell.

In the manufacture of the anode cermet for SOFC, they usually come from YSZ and NiO powder materials, a mixture of which is formed into a compact electrode in various ways. Next, NiO is reduced to metallic nickel under the influence of fuel in the fuel cell. For thin layers (for example, 100 microns thick) of nickel cermet annealed in air, it takes only a few minutes to complete the NiO reduction process at a temperature of 1000 ^o C.

 Closest to the present group of inventions in terms of manufacturing a cermet fuel electrode according to the technical essence and the achieved result when using is a method of manufacturing a cermet fuel electrode, which consists in applying a separate electrically conductive layer to an external porous electrode connected to a solid ion-conducting electrolyte, which, in turn, is in contact with the internal electrode, including the introduction into the external porous electrode of a mixture consisting mainly of salt, soda the first metal, wherein the metal-containing component is selected from nickel, cobalt and a mixture thereof, and the salt is selected from nitrate, acetate, propionate, butyrate and a mixture thereof, or a mixture thereof consisting mainly of a salt containing a second metal wherein the metal-containing component is selected from cerium, strontium titanate and mixtures thereof, and the salt is selected from nitrate, acetate, propionate, butyrate and mixtures thereof, as well as a non-ionized surfactant, heating the applied mixture in the atmosphere to a temperature sufficient to form a separate solid an electrically conductive porous multiphase layer consisting mainly of a conductive oxide selected from the group consisting of cerium oxide, strontium titanate and mixtures thereof, fine metal particles contained therein, preferably selected from the group consisting of individual nickel particles, individual cobalt particles and mixtures thereof, while the particles have a diameter of from 0.05 to 1.75 μm.

 In addition, the external porous electrode contains large metal particles with a diameter of from 3 to 35 μm, partially embedded in the base structure, including stabilized zirconia and thin metal particles having a diameter of from 0.25 to 0.75 μm.

In addition, the dopants used with the second metal contained in the salt are selected from the group consisting of Mg, Sr, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb , Y, Al, and mixtures thereof, and their heating is carried out at a rate of from 50 to 100 ^o C per hour (US patent N 5021304, CL H 01 M 8/10, publ. 1991).

The disadvantage of this method of manufacturing the anode is multi-stage and a large number of used organic reagents of various classes. The present invention allows the formation of a fuel electrode in one operation using one physicochemical process and one class of organic reagents, namely a mixture of dimethylcarboxylic acids, in which a straight carbon chain can be represented next to from C ₁ to C ₁₂ . This combination of carboxylic acids is the cheapest and most widespread in the large-tonnage production of organic reagents.

 The electrical insulating layer is one of the necessary elements of the design of VTTE. For the operation of VTTE, it is necessary to provide electrical insulation between the electrolyte, the anode and the current passage. The insulating material in the designs of VTTE is in contact with the electrolyte and the materials of the anode and cathode. In this regard, the most stringent requirements are imposed on the contacts of the insulating material, namely, such contacts must maintain mechanical strength and gas tightness under operating conditions, exclude the interaction of materials, which can lead to loss of operability of VTTE.

 The most common requirement for an insulating material is the stability of the structure and its characteristics at high temperatures, reliable contact with mating materials, the absence of interaction in the contact zone and the proximity of the KTR value of the insulating material and the KTP of the mating materials.

Acceptable insulating properties are ceramic materials based on magnesia spinel Al ₂ O ₃ and / or MgO (German patent N 2756172, class C 25 B 9/04, publ. 1979).

 A sufficiently low electrical conductivity characterizes solid electrolytes based on zirconium dioxide with a high content of stabilizing additives and chemical compounds of zirconium, for example, zirconates, which makes it possible to use them as electrical insulating materials. In addition, the value of their thermal expansion coefficient coincides well with the thermal expansion coefficient of solid zirconium electrolytes.

 Under conditions of operating temperatures of VTTE operation, doped magnesian spinels possess good electrical insulating properties, as well as other listed properties. Doping, as a rule, is carried out in order to approximate the KTP of the materials of the VTTE components mated to an electrical insulator (electrolyte, electrode, current passage). In the technology of manufacturing a VTTE cell, the operation of applying the insulating layer is actually the final operation, after which the cell is ready for placement on the stack, i.e. It is not possible to exceed the temperature of the formation of previous layers (components) of VTE. At the same time, the sintering temperatures of the materials of the insulators are relatively high. The use of additives to obtain fusible eutectics in this situation is unacceptable, because all of them easily diffuse into the VTTE components mating with the electrical insulator and violate their functional properties.

 Closest to this group of inventions in terms of the manufacture of an insulating layer according to the technical essence and the achieved result when used is a method of manufacturing an insulating layer, which consists in preparing a mixture of components based on magnesia spinel using fusible eutectics (German patent N 2746172, class C 25 B 9 / 04, publ. 1979).

Thus, today we can consider the following sequence of arrangement and manufacture of VTTE components to be rational:
- bearing porous cathode;
- a layer of electrode material with a thickness of not more than 0.6 μm, contributing to the activation of electrode processes deposited on a porous base of a bearing electrode material;
- current passage;
- a gas-tight layer of Ce (Sm / Gd) O _2-x with a thickness of 5 - 10 μm, on the surface of the active electrode material in contact with MLS, acting as an electrolyte;
- a gas-tight YSZ layer on the Ce (Sm / Gd) O _2-x surface with a thickness of 3-5 microns to prevent the recovery of doped cerium oxide (electrolyte) with fuel gases;
- cermet fuel electrode;
- electrical insulating layer.

 The basis of this group of inventions is the task of creating a universal method of manufacturing VTFC and its components, which allows producing a cathode, electrolyte, anode, current passage, electrical insulating and interface layers in various variations within a single technological process, while reducing the specific energy costs for manufacturing VTFC, the range of used reagents and equipment.

The problem in relation to the method of manufacturing a single VTTE with the achievement of the above technical result is solved by the fact that in the known method of manufacturing VTTE, including the manufacture of a cathode, deposition of an electrolyte and anode, followed by heat treatment of the entire structure of VTTE, an interface layer, current passage, electrolyte are applied after the cathode is manufactured based on doped cerium oxide, an electrolyte based on doped zirconium oxide, and then the anode and the insulating layer, using one device, and for gotovleniya all applied, mating components and sintered in a high temperature fuel cell main prepared organometallic complex characterized by the general formula
[CH ₃ - (CH ₂ ) _n - C (CH ₃ ) ₂ - CO ₂ ] _m Me ^{+ m} ,
where n = 1 - 7,
and additional, in special cases:
[C _n H _{2n + 1} O] _m Me ^{+ m} ,
where n = 2 - 8,
m is the valency of the metal,
Me - chemical elements: Mg, Ca, Sr, Ba, Al, Sc, Y, In, La and lanthanides, Ti, Zr, Hf, Gr, Mn, Fe, Co, Ni, Cu, occurring in the form of metals or their oxides the composition of materials used to form the cathode, anode, current paths, electrolytes, interface and electrical insulating layers.

 In addition, in the manufacture of the cathode, organometallic complexes corresponding to the metal component are used as a binder for mixing the moldable mass of the cathode.

 In the process of manufacturing a current passage, an electrolyte, an interface layer, an insulating layer, organometallic complexes corresponding to the metal component are used as the liquid phase of organic carriers of solid phases of the corresponding finely dispersed powder materials for the manufacture of current passages, electrolytes, interface and insulating layers, or directly in the form of a liquid phase, those. without the addition of powder materials. The choice depends on the chemical properties of a particular applied material.

 In the process of manufacturing the anode, the organometallic complex is used as the liquid phase in the manufacture of the paste mixture, comprising a coarse and fine dispersion of the ion-conducting and electron-conducting corresponding powder materials that make up the anode cermet.

The essence of the invention lies in the use of metal carboxylates, mixtures of metal carboxylates, alcoholates of the same metals and their mixtures, compounds of metal carboxylates with alcoholates, during thermal decomposition of which (in atmospheric oxygen) or during thermal dissociation of which (in an inert atmosphere, without decomposition of organic radicals transforming into a gaseous state), oxide materials of the required phase and chemical composition are synthesized. The synthesis occurs at relatively low temperatures (300 - 600) ^o C, i.e. in the range of decomposition temperatures of carboxylates and alcoholates, and, according to data confirmed by x-ray structural analysis, leads to the formation of the material of the necessary crystalline structure.

 At the time of synthesis, oxide materials have a high chemical activity, which leads to their sintering at low temperatures at the time of formation of the components of the HTFC.

 The selection of carboxylates and alcoholates is carried out on the basis of the temperature range of the beginning and end of their decomposition, which should optimally coincide with the synthesis temperature of the oxide material applied, and the decomposition process (dissociation for acylates) should not have sharp endothermic and exothermic effects. In this case, both individual carboxylic acids and mixtures thereof, alcoholates and mixtures thereof, and compounds of alcoholates with carboxylates can be used.

In FIG. Figure 4 shows the curves of the stereographic analysis of the high-temperature dissociation of the zirconium salt of dimethylbutylacetic acid, zirconium acetylacetonate and zirconium butylate in nitrogen. From the presented DTG diagram it follows that weight loss during decomposition of zirconium acetylacetonate continues even at temperatures above 700 ^o C. The decomposition of zirconium dimethylbutylacetic salt ends at a temperature of 530 ^o C, and zirconium butylate at a temperature of 380 ^o C.

From the DTG in FIG. 4 it follows that zirconium butylate has a lower decomposition temperature (below 400 ^° C.) of the chemical compounds shown and a higher zirconium content, which contributes to a high deposition rate of the ZrO ₂ / Y ₂ O ₃ film.

Термограммы разложения соединений диметилбутилуксусного циркония с бутилатом циркония в сравнении с чистым бутилатом циркония и с чистым диметилбутилуксусным цирконием представлены на фиг.5.The compounds of zirconium butylate with its acylates were also tested:
Zr (OBu) (OCOR) ₃ - 1 _Bu : 3 _Ac (3 ¹ )
Zr (OBu) ₂ (OCOR) ₂ - 2 _Bu : 2 _Ac (3 ² )
Zr (OBu) ₃ (OCOR) - 3 _Bu : 1 _Ac (3 ³ )
In the compound (3 ¹ ) there are few butoxy groups, which means that the zirconium content increases slightly. Compounds of composition (3 ² ) and (3 ³ ) with a high content of zirconium. In all three of the above compounds containing zirconium butylate, there is an acceptable character of high-temperature joint decomposition (dissociation for acylates) groups:

Thermograms of the decomposition of compounds of dimethylbutylacetic zirconium with zirconium butylate in comparison with pure zirconium butylate and with pure dimethylbutylacetic zirconium are presented in FIG. 5.

All thermograms were obtained in a nitrogen atmosphere. As can be seen from a comparison of the obtained thermograms, the compounds of zirconium butylate with an extract of zirconium dimethylbutylacetic acid decompose at different temperatures: 530 ₄ ; 470 _{2: 2} ; 435 _{3: 1} ; 380 _Bu ^o C. However, for compounds of composition (3 ² and 3 ³ ), the DTA lines (2; 3) are more direct than for individual zirconium butylate or zirconium dimethylbutyl acetate. This means that for compounds of the composition (3 ² and 3 ³ ), in the absence of sharp exothermic and endothermic effects, the application process is more stable, i.e. The substrate temperature set by the technology is not subject to fluctuations due to endo- and exothermic effects, which, in turn, contributes to the high-quality deposition of a gas-tight solid electrolyte on the substrate.

где M^A - металл с валентностью А,
M^B - металл с валентностью В,
m = 2 - 8;
n = 6 - 12;
x + y = A;
α+β = B
Далее на нагретую подложку приготовленную смесь соединений наносят окрашиванием, напылением, накаткой или другими способами в инертной атмосфере (N₂, Ar, CO₂) или атмосфере воздуха. Температура нагрева подложки и атмосфера, в которой проводят нанесение, зависят от конкретных элементов металлов в составе исходной смеси.For the manufacture of thin-film electrolyte from initial mixtures of carboxylates, mixtures of compounds of the type are prepared:

where M ^A is a metal with a valency A,
M ^B - metal with valency B,
m is 2-8;
n is 6-12;
x + y = A;
α + β = B
Next, on the heated substrate, the prepared mixture of compounds is applied by coloring, spraying, knurling or other methods in an inert atmosphere (N ₂ , Ar, CO ₂ ) or air. The heating temperature of the substrate and the atmosphere in which the application is carried out depend on the specific elements of the metals in the composition of the initial mixture.

 The basis of this group of inventions with respect to the cathode is the task of creating a method for manufacturing a VTTE supporting porous ceramic cathode, which allows varying the strength and structural characteristics of the porous cathode over a wide range while reducing the energy cost of sintering the material.

The problem with the method of manufacturing the cathode with the achievement of the above technical result is solved by the fact that in the method of manufacturing a supporting ceramic cathode VTTE, including the synthesis of a powder of an electrode material - doped lanthanum manganite, preparation of the moldable mass with an organic binder component, the formation of the carrier base with its subsequent sintering , the synthesis of powder of electrode material is carried out by the joint deposition of carbonates from their nitrate solutions, followed by their synthesizing firing, and as an organic binder component for the synthesized powder of the electrode material, carboxylates of chemical elements: La, Cr, Mn, Co, Ni, doped with elements from the group of alkaline-earth elements are used, and the formation of the supporting ceramic cathode is carried out by isostatic pressing followed by sintering a temperature of 1100 - 1380 ^o C. To achieve non-shrinking sintering of the cathodes from a powder of electrode material characterized by the formula La _x A _1-x MnO ₃ , where A is Mg, Ca, Sr, Ba; 0.6 ≤ x ≤ 1, or a mixture of them synthesizing the firing of co-precipitated carbonates of these elements is carried out at a temperature not exceeding 1380 ^o C. To prepare an organic binder component based on metal carboxylates, acids with the general formula C _n H _2n O _{2 are used} where n = C ₆ - C ₁₂ . The total mass of the binder is 3 to 15 wt.% In relation to the prepared molded mass. The total concentration of metals in the mixture of carboxylates is in the range (10 - 360) g / kg.

After decomposition, the binder forms a compound of the composition: La _y Sr _1-y MnO ₃ , La _y Sr _1-y CoO ₃ , La _y Sr _1-y CrO ₃ , La _y Sr _1-y NiO, where 0.6 ≤ y ≤ 1 , 0. Sintering of the cathodes is carried out in a furnace in a vertical position at a temperature of 1100 - 1380 ^o C.

The essence of the invention lies in the use of a binder during the formation of the cathode from the initial powder, which forms a material identical to the material of the initial powder (cathode) during thermal decomposition (during sintering). As a result of this, the sintering of the product begins already at the burning temperatures of the binder 300-600 ^° C, due to the oxidation of the metal components of the carboxylates and the simultaneous synthesis of the cathode material from them in the interparticle space of the initial strontium manganite-lanthanum powder.

 Carboxylates in the process of manufacturing the moldable mass perform the function of a plasticizer and a binder, and during sintering, they also play the role of a blowing agent (due to the burning out of the organic component).

 Thus, the features of this cathode manufacturing method are the use of metal carboxylates as a binder during cathode molding, forming a highly sintering material similar to the cathode material during the burning of the binder and sintering the cathode, which allows simultaneous binder and sintering processes at lower temperatures, than the synthesis of the initial powder of manganite-lanthanum-strontium. The use of the carboxylates described above as a binder plasticizer and pore former reduces the coefficient of shrinkage during sintering from 18 - 20% to 0.5 - 3%. The choice of carboxylic acids in this case is based on the possibility of obtaining carboxylates with a high metal content.

 The basis of this group of inventions in terms of the interface layer is the task of manufacturing VTTE, in which the chemical interaction between the mating components at operating temperature conditions is minimized, and thereby the stability of materials in working gas environments is increased, i.e., ultimately, the resource of VTTE. Depending on the functional purpose of the interface layer, materials with both electrode properties and electrolyte properties can be used in their manufacture. Moreover, each interface layer has two (sometimes more) functions: an electrode and an interface layer that activates the electrode reaction; electrolyte and anti-diffusion interface layer; electrolyte, a protective coating of the previous layer (for example, from a reducing medium of fuel gas) and a transition buffer combining KTP of adjacent layers; etc. Since the required thickness of the layers does not exceed units of micrometers, the most rational way to form them is the pyrolysis decomposition of chemical compounds of metals with organic reagents, where metals are selected from the group constituting one or another interface layer, and organic reagents are selected from the group of dimethylcarboxylic acids, radicals which are easily thermally dissociated without noticeable decomposition of the radicals themselves under the conditions of deposition of the interface layers, and / or, organic reagents are selected from PPA of alkyls supplementing dimethylcarboxylic acids to prevent sharp exo and endothermic effects under the conditions of the thermal dissociation reaction when applying the interface layers.

The problem with the method of manufacturing the interface layers with the achievement of the above technical result is solved by the fact that in the method of manufacturing the interface layer, including the synthesis of the organometallic complex, applying it to a heated substrate, a compound characterized by the formula is used as the applied material of the organometallic complex
Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _x (OC _m H _{2m + 1} ) _AX ,
where Me are metals selected from the group: Cr, Mn, Co, Ni, Cu, Y, Zr, La and lanthanides, Mg, Ca, Sr, Ba;
A is the valency of a given chemical element (metal);
X is the coefficient determined from the inequality 0 <X <A;
n is 1 to 7;
m is 2-8;
and also the fact that for the manufacture of a gas-tight film of the interface layer using a mixture of compounds characterized by the General formula
Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _AX (OC _m H _{2m + 1} ) _X ,
where X = 0;
Me - metals selected from the group: Mg, Ca, Sr, Ba, Ce, Pr, Sm, Gd, Er,
the total metal content in the mixture of compounds is not more than 20 g / kg, and the deposition is carried out on a substrate heated to a temperature of not more than 530 ^o C in air with the formation of a gas-tight film of the interface layer with a thickness of not more than 0.6 μm based on doped chromite electrode reaction activating lanthanum; and also the fact that for the manufacture of a gas-tight film of the anti-diffusion interface layer, a mixture of compounds is used, characterized by the general formula:
Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _AX (OC _m H _{2m + 1} ) _X ,
where X = 0;
Me - metals selected from the group: Ce, and doping elements Sm, Gd;
n = 1, 2,
the total metal content in the mixture of compounds is not more than 20 g / kg, and the mixture is applied on a substrate heated to a temperature of not higher than 380 ^o C in an inert gas atmosphere with the formation of a gas-tight anti-diffusion film of the interface layer with a thickness of not more than 10 μm based on doped cerium oxide; and also the fact that for the manufacture of the interface layer that protects the previous layer from the reducing gas environment, use a mixture of compounds characterized by the General formula
Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _AX (OC _m H _{2m + 1} ) _X ,
where Me are metals selected from the group: Zr, Y, La and lanthanides,
A is the valency of a given chemical element (metal);
X - can take the values 1, 2, 3, ... A,
the total content of zirconium and doping components in the mixture is not more than 50 g / kg, and the application of the mixture is carried out by coloring the substrate, heated to a temperature of not higher than 430 ^o C, in an inert gas atmosphere with the formation of a protective interface layer, a thickness of not more than 5 microns , based on doped zirconia, moreover, either Ar, or N ₂ , or CO ₂ is used as an inert gas atmosphere.

 The basis of this group of inventions in terms of the current passage is the task of creating a method of manufacturing a current passage, providing a technology for manufacturing a current passage, free from the noted drawbacks, allowing to obtain current paths with strength, structural and electrical characteristics that vary widely. In addition, for the manufacture of the current passage, it is proposed to use the starting components and materials similar to the materials used for the manufacture of the remaining components of VTTE, as well as within the framework of a uniform technological process and equipment.

 This allows you to significantly reduce the range of materials used, reagents, technological equipment and, as a result, reduce energy costs for manufacturing.

The task in relation to the method of manufacturing a VTTE current passage with the achievement of the above technical result is solved by the fact that it includes the synthesis of a powder of an electronically conductive material based on doped lanthanum chromite, the manufacture of an ultrafine mixture from synthesized powder in organic media and its application to a supporting cathode with subsequent heat treatment. A fine dispersion is made by grinding the synthesized powder of the electronically conductive material of doped lanthanum chromite to an ultrafine state in a liquid medium of a mixture of organometallic complexes of chromium, lanthanum and doping elements. The current passage film is made by repeatedly applying a fine dispersion to the surface of the supporting cathode, heated to the temperature of formation of a mixture of organometallic complexes of chromium, lanthanum and doping elements of a gas-tight film of doped lanthanum chromite of the same composition as the finely divided powder synthesized separately. In the manufacture of the VTTE current passage, pyrolysis decomposition of the organometallic complexes of the corresponding elements included in the current passage is used. For the manufacture of a carrier of fine dispersion of powders of doped lanthanum chromite, lanthanum carboxylates and doping elements are synthesized, characterized by the formula
Me ^{+ M} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _m ,
where Me is Cr, La, Sr, and / or Ca, and / or Mg;
m is the valency of the metal;
n = 1 - 7.

 The concentration of Cr, La, Sr, Ca, Mg in the mixture of carboxylates is in the range from 20 to 110 g / kg. The ratio of solid to liquid phases in the manufactured fine dispersion is in the range (1/100 - 15/100) of the mass.

A current passage is applied to a fabricated carrier air electrode from MLS by coloring, rolling or spraying at atmospheric pressure in an air or inert atmosphere. In this case, the electrode surface is heated to a temperature sufficient to decompose the mixture of Cr, La carboxylates and doping elements and form a material corresponding to the compound La _1-x Me _x CrO ₃ , where Me is the doping element.

To increase the speed of formation of the current passage, an ultrafine mixture prepared on the basis of doped lanthanum chromite powder and a mixture of liquid carboxylates of the same elements is used as the applied material. In this case, the growth rate of the gas-tight film of the current passage on the surface of the supporting porous cathode increases by two to three times and is at least 60 μm per hour. An ultrafine mixture is made by grinding a powder of doped lanthanum chromite to a homogeneous state in a liquid medium of chromium carboxylates, lanthanum and doping additives. The temperature of the formation of the current passage from doped lanthanum chromite on the surface of the supporting cathode does not exceed 600 ^o C.

 The basis of this group of inventions in terms of the electrolyte is the task of creating a universal method of manufacturing a solid oxide electrolyte, which allows varying the strength and structural characteristics of the electrolyte over a wide range, while reducing the energy cost of sintering the material.

 In addition, the method in accordance with this invention allows the manufacture of solid oxide electrolyte in the framework of a single technology for the manufacture of a single VTE. This greatly simplifies tooling, equipment, and also reduces the range of materials used, reagents in the manufacture of solid oxide electrolyte.

с образованием смеси карбоксилатов металлов, или смеси алкоголятов металлов, или смеси карбоксилатов и алкоголятов металлов,
где Me - любой из металлов, входящий в функциональный компонент ВТТЭ;
A - валентность данного химического элемента (металла);
X - коэффициент, определяемый из неравенства 0 < X < A;
n = 1 - 7;
m = 2 - 8.The problem with the method of manufacturing an electrolyte with the achievement of the above technical result is solved by the fact that in the method of manufacturing a solid oxide electrolyte VTTE, which consists in the preparation of the starting organometallic compound, including the preparation of aqueous solutions of salts of chemical elements, the extraction of individual chemical elements from their aqueous solutions with an organic reagent or a mixture thereof, mixing the prepared individual metal extracts, drying the extract salts formation of a moldable mass, heating the ceramic electrode to a predetermined temperature, applying the prepared organometallic compound to the electrode surface and subsequent heat treatment of the ceramic electrode with the organometallic compound applied, while the organometallic compound for the manufacture of a solid oxide electrolyte is synthesized using the reaction:

with the formation of a mixture of metal carboxylates, or a mixture of metal alcoholates, or a mixture of metal carboxylates and alcoholates,
where Me is any of the metals included in the functional component of VTE;
A is the valency of a given chemical element (metal);
X is the coefficient determined from the inequality 0 <X <A;
n is 1 to 7;
m = 2 - 8.

To prepare the organometallic compound (3), the synthesis of metal carboxylates (1) is carried out by liquid and / or solid-phase extraction of the corresponding metals (Me ^{+ A} ) from aqueous solutions of their salts and / or suspensions of their carbonates or hydroxides precipitated from solutions of salts of mineral acids. And the synthesis of zirconium alcoholate (2) Zr (OC _m H _{2m + 1} ) _{4 is} carried out in the process of interaction of the mineral zirconium salt with alcohol and metallic calcium by boiling the mixture in a flask under reflux until the calcium is dissolved. The mixture of the starting components during the preparation of the organometallic compounds is carried out at a temperature of 80 - 100 ^o C.

The organometallic zirconium compound (3) or (2) or (1), prepared as described above and modified with at least one of the elements Mg, Ca, Sc, Y, Ce and / or lanthanides, is applied to the surface of the supporting cathode by rolling, staining or spraying a gas-liquid emulsion, scanning a means applying the prepared composition over the surface of the cathode at a temperature of a heated electrode of 400 - 550 ^o C. Moreover, the growth rate of the layer thickness is 10 - 40 μm / h.

 To increase the rate of deposition of an electrolyte film, a powder of modified zirconium dioxide is added to the applied composition of the prepared organometallic compound, in which 95% of the particles have a size of less than 2 microns and in an amount of 0.1 - 2.0 wt.%.

 The process of applying an organometallic compound to the heated surface of a ceramic electrode is carried out in an inert medium.

To obtain a proton electrolyte, a mixture of metal carboxylates is prepared, characterized by the formula
SrCe _0.85 Gd _0.15 (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) ₆
or
BaCe _0.85 Gd _0.15 [O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ] ₆
where n = 2 - 3,
applied to the surface of the electrode, preheated to a temperature not exceeding 470 ^o C, decomposes under the influence of temperature with the formation of a proton electrolyte composition BaCe _0,85 Gd _0,15 O ₃ or SrCe _0,85 Gd _0,15 O ₃ .

The process of manufacturing a solid oxide electrolyte is completed by the fact that after applying the prepared organometallic compound to the heated electrode surface, the resulting half cell is subjected to heat treatment at a temperature of 900 - 1250 ^o C for 1 hour

 The basis of this group of inventions in terms of the cermet fuel electrode is the task of creating a method of manufacturing a cermet fuel electrode, which provides a technology for the production of a cermet electrode, free from the above-mentioned disadvantages, which makes it possible to manufacture a fuel electrode with a given porosity. In addition, the technology of its manufacture and the equipment used for this should be compatible with the technology and equipment used in the manufacture of a single VTTE as a whole.

 The problem in relation to the method of manufacturing a cermet fuel electrode with the achievement of the aforementioned technical result is solved by the fact that in the known method of manufacturing a cermet fuel electrode VTE, including forming on a solid electrolyte in contact with an internal air electrode, a cermet layer of an electrode consisting of a coarse electrically conductive material selected from the group of metallic nickel and / or cobalt, a coarsely dispersed ion-conducting material based on d carbonated zirconia and / or doped cerium oxide and the subsequent formation on the coarse-dispersed layer of a separate finely divided electrically conductive porous multiphase layer consisting of a metal material selected from the group of nickel and / or cobalt, ion-conductive doped material based on cerium oxide, by applying and subsequent heating the mixture -pastes consisting of the above-mentioned finely dispersed components with a binder, a cermet fuel electrode is made by simultaneously forming by coarse and finely dispersed components of the porous multiphase layer by applying a paste mixture to an electrolyte in contact with the internal air electrode.

In this case, a paste mixture is prepared by mixing powders of a coarse electrically conductive material selected from the group of metallic nickel and / or cobalt, coarse ion-conductive material based on doped zirconium dioxide and / or doped cerium oxide, finely dispersed ion-conductive material based on doped cerium oxide and the liquid phase of nickel carboxylates and / or cobalt characterized by the general formula
Me ^{+ m} (O ₂ CC (CH ₃ ) ₂ - (CH ₂ ) _n -CH ₃ ) _m ,
where Me is Ni and / or Co,
m is the valency of the metal,
n = 1 - 7,
which during heat treatment forms an electrically conductive porous multiphase layer, fastening together coarse and finely dispersed phases that form the cermet of the fuel electrode.

 In addition, the ratio of solid to liquid phases in the manufactured paste is in the range of - (1/3 - 5/7) mass.

 The concentration of nickel and / or cobalt in liquid carboxylates should be in the range from 20 to 70 g / kg of carboxylate, and nickel and / or cobalt powder is added in the ratio: the amount of metal powder to the amount of electrolyte powder is 1.1 / 1.0.

Coarse particles of nickel and / or cobalt powder should have a regular spherical structure with a diameter of 10 to 15 μm, and the synthesized coarse powder of the electrolyte should have a threadlike shape, and the ratio of the particle length to its diameter should be at least 10 with a particle diameter of 5 - 10 μm. At the same time, fine powder of doped cerium oxide contains 90% of particles with a diameter of less than 1.0 microns. Application of the paste mixture is carried out by coloring in air at room temperature and atmospheric pressure. Semi-element coated with a crude mixture of paste is subjected to heat treatment in vacuum at a temperature of not higher than 400 ^o C and a residual pressure of not more than 0.1 ATM.

 The basis of this group of inventions in terms of the electrical insulating layer is the task of creating a method for manufacturing VTFC, which provides the most effective electrical insulation between its components (current passage and anode, electrolyte and fuel gas medium) to prevent spurious current connections between the electrodes.

The problem in relation to the method of manufacturing an insulating layer with the achievement of the aforementioned technical result is solved by the fact that in the method of manufacturing an insulating layer, comprising preparing a mixture of components based on magnesia spinel, the second component in the prepared applied mixture uses a mixture of organometallic complexes with the general formula
Me ^{+ A} [(O ₂ CC (CH ₃ ) ₂ - (CH ₂ ) _n -CH ₃ ) _1-x (OC _m H _{2m + 1} ) _x ] _A ,
where n = 1 - 7,
m = 2 - 8,
Me - Mg, Al, Zr, Y, Ca, La and lanthanides,
A is the valency of the metal,
x - can take values from 0 to 1, depending on which method is applied: staining or spraying from a gas-droplet emulsion.

For the manufacture of an insulating layer by the method of coloring, a dispersion is used consisting of 30% of the powder material and 70% of the liquid phase. The powder material is magnesia spinel of the composition MgAl ₂ O ₄ with 15% addition of 9YSZ powder, and the liquid phase is a mixture of Al and Mg carboxylates, where the organic part of the carboxylates is dimethylbutylacetic acid. The weight ratio between aluminum and magnesium in the carboxylate mixture is designed to form a compound corresponding to MgAl ₂ O ₄ when they are calcined. The temperature of the insulated surface during application is maintained at a level not exceeding 600 ^o C.

A method of manufacturing an electrical insulating layer by the method of applying from a gas-droplet emulsion is implemented as follows. The organometallic salt of Al and Mg with the composition Mg [Al (Alc) ₄ ] ₂ is mixed with the carboxylates Zr and Y, where the organic part is represented by dimethylbutylacetic acid. Zirconium and yttrium carboxylates are added in an amount sufficient to form 5-15% stabilized zirconium yttrium in magnesia spinel after pyrolysis of the mixture on a heated electrically insulated surface. Application is made in the form of a strip with a width of 2 - 3 mm. The temperature of the electrically insulated surface during application is maintained at 450 ^o C. As a result, an electrically insulating layer with a thickness of 12 - 15 microns is formed, having a composition corresponding to the chemical formula
(MgAl ₂ O ₄ ) _1-n ((SrO ₂ ) _0.91 (Y ₂ O ₃ ) _0.09 ) _n ,
where n is 5 to 15 wt.%.

In FIG. 1 shows the main stages and the sequence of manufacturing the MLS and the material for applying the current passage; figure 2 - the main stages and sequence of manufacture of materials for applying electrolyte and cermet anode; figure 3 - the main stages of manufacturing a single VTE; figure 4 shows thermoanalytical curves of zirconium acetylacetonate (1), zirconium dimethylbutyl acetate (2) and zirconium butylate (3); figure 5 - thermoanalytical curves Zr (OBu) ₄ (1), Zr (OBu) ₃ (2MeBuAc) ₄ (2), Zr (OBu) ₂ (2MeBuAc) ₂ (3), Zr (2MeBuAc) ₄ (4) ; figure 6 - the surface of the cathode of MLS with varying degrees of increase; in FIG. 7 - installation for applying electrolyte to a tubular electrode; in FIG. 8 is a diagram characterizing the particle size distribution of YSZ powder; figure 9 is a layer of electrolyte YSZ on a porous cathode; figure 10 is a view of the powder (CeO ₂ ) _0.85 (Sm ₂ O ₃ ) O _0.15 with an increase of 28,000 times; figure 11 shows a fuel electrode, where: a) is a photograph of a YSZ powder of a fibrous structure, b) is a cermet anode structure, c) is a photograph of spherical particles of nickel powder.

In FIG. 1, 2, 3 shows the principal technological sequence of processes for the manufacture of VTTE. As noted earlier, carboxylates of individual metals or a mixture of individual metal carboxylates with the general formula of carboxylates are taken as a universal material, a metal carrier, which, after heat treatment, forms the materials of electrodes, interface layer, current passage, electrolyte, electrical insulation layer, diffusion barrier, etc. ₃ - (CH ₂ ) _n -C (CH ₃ ) ₂ -COO] _m Me ^{+ m} , where n = 1 - 8, and m is the metal valence.

 Metal carboxylates are mixed in such a way that the concentration ratios of these metals in the mixtures correspond to the given ones, i.e. those needed in formed electrolytes, electrodes, electrical insulating and interface layers, etc.

 Further, the prepared carboxylate mixtures are used in various versions, depending on the particular task being solved: the production of specific VTFC components.

 In the manufacture of supporting electrodes, carboxylates are used simultaneously as a plasticizer and blowing agent binder. Moreover, for the manufacture of a binder, the carboxylate mixtures are concentrated to the maximum possible value for these carboxylates. Then the powder is closed on this bundle and the part is molded from the press powder by pressing (bearing cathode, bearing anode, stack elements, etc.).

For the manufacture of a supporting cathode from MLS, a powder of composition La _0.7 Sr _0.3 MnO ₃ is prepared. In the manufacture of the binder take a mixture of carboxylic acids: dimethylpropylacetic, dimethylbutylacetic, dimethylamylacetic, dimethylhexylacetic and dimethylaurylacetic.

To a mixture of these acids, the carboxylates of individual metals La, Mn, Sr are obtained by extraction. After mixing, the carboxylate mixture is concentrated in vacuo at the required residual pressure and appropriate temperature to the maximum total metal concentration in the mixture. The concentrated mixture is mixed with La _0.7 Sr _0.3 MnO ₃ powder in a screw mixer in the presence of terpene. Then terpene is distilled off in vacuo. Cathodes are made by hydrostatic pressing and sintered in air. Some sintering results at various temperatures are given in Table 2. For the further manufacture of the elements, cathodes with an open porosity of ~ 36.6% and a pore size of 2 to 3 μm are selected (Fig. 6).

Next, an interface layer is applied to the cathode surface, which is a gas-tight film of the following composition:
La _1-x Me _x CrO ₃ , where Me is a doping element selected from the series Mg, Ca, Sr, Ba. For this, carboxylates of individual metals are prepared, mixed in accordance with the proportion necessary for the formation of the compound La _1-x Me _x CrO ₃ during their pyrolysis and applied to the preheated surface of the supporting cathode by coloring, spraying, gas-droplet emulsion or knurling. The total concentration of metals in carboxylates (in terms of oxides) is not more than 30 g / kg. The thickness of the resulting layer is not more than 0.6 microns. The temperature of the preheated when applying the surface is not higher than 530 ^o C.

A current passage made of strontium lanthanum chromite is applied to a cathode thus prepared with an interface layer. For its manufacture, a mixture of Cr, La, and Sr carboxylates with a concentration of not more than 110 g / kg (based on the total amount of oxides formed during calcination) is taken and ultrafine La _0.7 Sr _0.3 MnO ₃ powder is added to it with vigorous stirring. The ratio of the solid phase of the powder to the liquid phase of carboxylates is from 1/100 to 5/100 parts by weight. The prepared ultrafine mixture is applied to the preheated surface of the supporting cathode to a temperature sufficient to form a film of doped lanthanum chromite from the organometallic complex. In practice, the temperature of formation of the above-mentioned film does not exceed 530 ^o C. Application of the current passage to the surface of the supporting cathode can be carried out by staining it in a stream of nitrogen at atmospheric pressure, or by spraying an ultrafine suspension in an inert medium. In this case, the growth rate of the thickness of the gas-tight film of the current passage on the surface of the supporting porous cathode should be at least 20-60 μm per hour.

 Next, an electrolyte is applied to the cathode with the interface layer and current passage. For this, carboxylates of the necessary metals, alcoholates or mixtures thereof are used as starting organic reagents. The choice of a particular composition or mixture (carboxylates / alcoholates) depends on the chemical properties of the metals in the mixture.

For the manufacture of an electrolyte layer, which is a thin (5-10 μm) gas-tight film of the composition (CeO ₂ ) _0.85 (Sm ₂ O ₃ ) _0.15 or (CeO ₂ ) _0.85 (Gd ₂ O ₃ ) _0.15 used a mixture of carboxylates Ce / Sm or Ce / Gd, where the organic part of the carboxylates is represented by dimethylbutylacetic acid with a basic substance content of 97%. The application process is carried out at a surface temperature of not higher than 380 ^o C, by dyeing, rolling or spraying.

 As noted above, to protect the electrolyte based on doped cerium from reduction by anode gases, an electrolyte layer based on doped zirconia is made on its surface.

Dimethylbutylacetic acid and butanol are used as starting organic reagents for the manufacture of a material that makes it possible to deposit a thin-film oxide electrolyte based on 9YSZ. Zr and Y metal carboxylates are produced by liquid extraction, and zirconium butylate is produced by the reaction of zirconium sulfate with butanol and calcium metal. Yttrium is added to the prepared mixture in the form of carboxylate Y (2MeBuAc) ₃ . The thickness of the electrolyte is 3-5 microns.

For the manufacture on the element of the second electrode (anode), a paste mixture is used made from ion-conducting material (doped zirconia and / or doped cerium oxide), electron-conducting material (metal powder of nickel and / or cobalt) and metal carboxylates (nickel and / or cobalt ) For the manufacture of Ni / Co carboxylates, you can use a commercial mixture of carboxylic acids having the general formula HO ₂ CC (CH ₃ ) ₂ - (CH ₂ ) _n -CH ₃ , where n can take values from 1 to 7. The concentration of Ni / Co in carboxylates is not less than 70 g / kg (by the sum of metal oxides during calcination). In the composition of the paste mixture, the ratio of all solid components to liquid is (1/3 - 5/7) mass. Application of the anode is carried out on a heated surface by staining. The surface temperature is not higher than 380 ^o C.

 The last component in VTTE is an electrical insulating layer between the current passage and the anode on the surface of the electrolyte. Its necessity is due to the prevention of spurious current bonds between the electrodes and the elimination of the triple point effect - fuel gas / electrolyte / cathode in the places where the current passage is output.

For the manufacture of the insulating layer, a dispersion is used, consisting of 30% of the powder material and 70% of the liquid phase. The powder material is magnesia spinel of the composition MgAl ₂ O ₄ with 15% addition of 9YSZ powder, and the liquid phase is a mixture of aluminum and Mg carboxylates, where the organic part of the carboxylates is represented by dimethylbutylacetic acid. The weight ratio between aluminum and magnesium in the carboxylate mixture is designed to form a compound corresponding to MgAl ₂ O ₄ when they are calcined. The dispersion is applied by coloring on an insulated surface, heated no higher than 530 ^o C.

Thus, the manufacture of all applied components of VTTE is carried out on one installation (Fig.7) using one physicochemical process and one class of organic reagents - dimethylcarboxylic acids. The final operation of the manufacture of VTTE is sintering in air at a temperature not exceeding 1280 ^o C for an hour.

 A preferred embodiment of the invention for the manufacture of a cathode.

 In this example, the production of VTTE begins with the manufacture of a supporting ceramic cathode. For this, the powder of the electrode material is synthesized by the joint precipitation of carbonates from their nitrate solutions, followed by sintering. Then a moldable mass is prepared with an organic binder component containing Mn, La, or Co, La, or Cr, La, or Ni, La, doped with elements from the group of alkaline-earth elements. Next, the cathode of the press mass is formed by isostatic pressing and sintering.

 A ceramic cathode made in this way is the supporting element of the entire VTTE design.

 The inventive method solves the problem of manufacturing a supporting ceramic cathode with a given structure and strength with a significant reduction in heat treatment temperature and low values (0.5 - 3)% of the coefficient of shrinkage during sintering.

 The technical result achieved by the implementation of the inventive method of manufacturing a cathode is realized through the use of specially created material for the manufacture of the cathode. The material in the moldable mass simultaneously acts as a plasticizer, binder and blowing agent. As noted above, this allows you to get the product with a predetermined structure (not provided by the known technology) at substantially low sintering temperatures and shrinkage coefficients.

 As a result, the present invention provides a smaller range of starting materials, a uniform technological approach to obtain the necessary components with a higher yield and low energy consumption.

 The method is implemented as follows.

A powder of the composition La _x Sr _1-x MnO ₃ , where 0.6 ≤ x ≤ 1.0, is prepared, for example, by co-precipitation of La, Sr, Mn carbonates from their nitrate solutions, followed by filtration of the precipitate, drying, heat treatment, providing synthesis of the substance, and grinding.

 At the same time, a binder is prepared, which is a mixture of La, Sr, Mn carboxylates, for example, by liquid extraction method. The concentration of metals in the mixture is from 150 to 360 g / kg. Then prepare the moldable mass by mixing the prepared electrode powder with a binder, where the binder is 3 to 15 wt.%. The prepared mass is then molded, and the obtained cathode blank of the required shape is sintered.

 A cathode manufactured in accordance with the present invention fully complies with the technical characteristics given in specific embodiments of the present invention.

Example 1. A powder of the composition La _0.7 Sr _0.3 MnO ₃ was prepared by co-precipitation of La, Sr, Mn carbonates from nitrate solutions of these metals, filtering the resulting precipitate, drying and sintering it at a temperature of 1380 ^o C for 1 h The coarse cake obtained in this way was disaggregated in the mill to the specified aggregate size. X-ray phase analysis of the obtained powder confirmed the formation of a single-phase product of the primitive structure.

Carboxylates of individual metals were prepared by extraction of the corresponding metal with a mixture of carboxylic acids. In the preparation of carboxylates for a binder, a commodity mixture of carboxylic acids of the following composition was used, wt. %: dimethylpropylacetic acid C ₇ H ₁₄ O ₂ 36; dimethylbutylacetic acid C ₈ H ₁₆ O ₂ 31; dimethylamylacetic acid C ₉ H ₁₈ O ₂ 15; dimethylhexylacetic acid C ₁₀ H ₂₀ O ₂ 7; dimethyl lauryl acetic acid C ₁₂ H ₂₄ O ₂ 2.

 Some metal concentrations in carboxylates are shown in Table 1.

The obtained individual extracts were mixed in the desired ratio. In this example, a mixture of La, Sr, Mn carboxylates was used, corresponding to the composition: La _0.7 Sr _0.3 MnO ₃ and a total metal concentration of 210 g / kg.

La _0.7 Sr _0.3 MnO ₃ powder was mixed with a solution of carboxylates in a weight ratio of 93: 7. The mixture was prepared in a screw mixer for 1 hour. The resulting mixture was used to obtain tubular-shaped air electrodes by hydrostatic pressing. Then the tubes were sintered at various temperatures in air. The results are shown in table.2.

Example 2. A mixture of La _0.7 Sr _0.3 MnO ₃ powder and a solution of La, Sr, Mn carboxylates was prepared as described in Example 1. The resulting mixture was heated in air to a temperature of 650 ^{° C.} for 45 minutes. The resulting powder was disaggregated to destroy fragile aggregates formed after heat treatment. Further operations for the manufacture of tubular cathodes are similar to those described in example 1. The sintering temperature of the tubes was 1380 ^o C. The results of changes in the strength of the products are shown in table.3.

Example 3. The powder of the composition La _0.7 Sr _0.3 MnO ₃ used in examples 1 and 2 was mixed with a mixture of carboxylates containing Co, La, Sr in proportions corresponding to the composition La _0.6 Sr _0.4 CoO ₃ . These carboxylates were obtained by extraction of the corresponding metals. The total concentration of metals was 291 g / kg. The manufacture of the tubes was carried out as described in example 1. The results of sintering of the tubes at different temperatures are given in table 4.

 A preferred embodiment of the invention for the manufacture of an interface layer.

Example 4. For the manufacture of the interface layer on the supporting porous cathode of MLS made according to example 1, a CLS film 0.3-0.6 μm thick is applied. The application is carried out by coloring heated to 530 ^o With the surface of the cathode with a mixture of carboxylates Cr, La, Sr in an atmosphere of air. The total concentration of Cr, La, Sr in the mixture of carboxylates (in terms of oxides) was 20 g / kg. The organic part of the carboxylates is represented by a mixture consisting of, by weight. %: dimethylpropylacetic acid (C ₇ H ₁₄ O ₂ ) 36; dimethylbutylacetic acid (C ₈ H ₁₆ O ₂ ) 31; dimethylamylacetic acid (C ₉ H ₁₈ O ₂ ) 15; dimethylhexylacetic acid (C ₁₀ H ₂₀ O ₂ ) 7; dimethyl lauryl acetic acid (C ₁₂ H ₂₄ O ₂ ) 2.

The ratio of Cr, La, and Sr oxides after decomposition of the carboxylate mixture on the heated cathode surface corresponds to La _0.7 Sr _0.3 CrO ₃ material. After several (30 - 50) passes of staining, the film thickness reaches 0.5 - 0.7 microns.

Example 5. Next, the heating temperature of the cathode with the CLS layer deposited is reduced to 380 ^{° C.} and a layer of (CeO ₂ ) _0.85 (Gd ₂ O ₃ ) _0.15 from a mixture of Ce and Gd carboxylates, where organic part of the carboxylates is represented by dimethylbutylacetic acid 97 wt.%. The sum of the concentrations of Ce and Gd in the mixture of carboxylates (in terms of oxides) is 55 g / kg. After several (80-100) passes of staining, a (CeO ₂ ) _0.85 (Gd ₂ O ₃ ) _0.15 film of 5-10 microns thick is formed over the CLS film.

Example 6. Then, the heating temperature of the cathode with the deposited layers of CLS and (CeO ₂ ) _0.85 (Gd ₂ O ₃ ) _{0.15 is} increased to 410 ^{° C.} and a layer of 9YSZ is formed in a nitrogen atmosphere. The 9YSZ layer is applied from a mixture of organometallic compounds Zr (OBu) ₂ (2MeBuAc) ₂ + Y (2MeBuAc) ₃ with a concentration of Zr and Y (in terms of the sum of oxides) (30-50) g / kg. After several (60 - 80) passes of staining, a 9YSZ layer with a thickness of 3-5 microns is formed.

 A preferred embodiment of the invention is the manufacture of a current passage.

The method is implemented as follows. Carboxylates of individual metals are prepared. Next, the carboxylates of the individual metals are mixed in accordance with the proportion necessary for the formation of the compound La _1-x Me _x CrO ₃ , where Me is a doping element, during their pyrolysis.

After that, an ultrafine mixture is prepared from the synthesized separately prepared powder of the electrically conductive material La _1-x Me _x CrO ₃ and a mixture of carboxylates with a ratio of the solid phase of the powder and the liquid phase of carboxylates in the range of 1/100 - 5/100. The prepared ultrafine mixture is applied to the preheated surface of the supporting cathode to a temperature sufficient to form a film of doped lanthanum chromite from the organometallic complex. In practice, the temperature of formation of the above-mentioned film does not exceed 530 ^o C. The current passage can be applied to the surface of the supporting cathode by staining in a stream of nitrogen at atmospheric pressure, or by spraying an ultrafine suspension in an inert medium. In this case, the growth rate of the thickness of the gas-tight film of the current passage on the surface of the supporting cathode is 20-60 μm per hour.

 Example 7. A mixture of carboxylates of Cr, La and Sr is prepared analogously to its preparation in example 1 using the same organic reagents. The initial compositions of the individual components according to the metal content are shown in table 1.

When the mixture is calcined, a chromite-lanthanum-strontium compound of the following composition is formed: La _0.8 Sr _0.3 CrO ₃ . The mixture is applied to the porous surface of the supporting cathode, made in the form of a tube, heated to 530 ^o With in a stream of nitrogen. On the surface of the tube, a gas-tight current path of 3 mm wide is formed. The growth rate of the current passage film is 25-30 microns per hour.

Example 8. Unlike example 4, a powder of the composition La _0.8 Sr _0.3 CrO ₃ , in which 90% of particles with a diameter of less than one micron, is added to the mixture of carboxylates of Cr, La, and Sr. The amount of added powder is 1 wt.% To the mass of carboxylates. Then the prepared mixture is applied to the surface of the supporting cathode, as described in example 4, while the growth rate increases and is 60 μm per hour.

 Preferred embodiments of the invention for the manufacture of electrolyte.

где M^A - металл с валентностью A,
M^B - металл с валентностью B,
m = 2 - 8,
n = 6 - 12,
x + y = A,
α+β = B
Далее на нагретую подложку приготовленную смесь соединений наносят напылением, окрашиванием или другими способами в инертной атмосфере (N₂, Ar, CO₂). Температура нагрева подложки зависит от конкретных элементов металлов в составе исходной смеси. На фотографии (фиг.7) показано устройство для нанесения тонких оксидных пленок методом окрашивания в момент изготовления электролита.For the manufacture of thin-film electrolyte from initial mixtures of carboxylates (Zr / Y), a mixture of compounds of the type is prepared:

where M ^A is a metal with a valency A,
M ^B - metal with valency B,
m = 2 - 8,
n = 6 - 12,
x + y = A,
α + β = B
Next, on the heated substrate, the prepared mixture of compounds is applied by sputtering, staining or other methods in an inert atmosphere (N ₂ , Ar, CO ₂ ). The heating temperature of the substrate depends on the specific elements of metals in the composition of the initial mixture. The photograph (Fig. 7) shows a device for applying thin oxide films by the staining method at the time of manufacture of the electrolyte.

 Example 9. As starting organic reagents for the manufacture of a material that allows the application of a thin-film oxide electrolyte based on 10YSZ, dimethylbutylacetic acid and butanol are used. Zr and Y metal carboxylates are produced by liquid extraction, and zirconium butylate is produced by the reaction of zirconyl sulfate with butanol and calcium oxide. Metal concentrations are shown in table 1.

Иттрий добавляют в изготовленную смесь в виде карбоксилата Y(2MeBuAc)₃. Смесь при прокаливании образует соединение кубической структуры, состав которой показан в табл.5 (поз.1).The starting compound for application is obtained by reaction

Yttrium is added to the prepared mixture in the form of carboxylate Y (2MeBuAc) ₃ . The mixture, upon calcination, forms a compound of a cubic structure, the composition of which is shown in Table 5 (item 1).

The material thus prepared is applied to the surface of the cathode tube of manganite-lanthanum-strontium. The surface temperature of the tube is maintained at 530 ^o C. The reaction is carried out in a stream of nitrogen. At the same time, a gas-tight film of a solid electrolyte of the composition - 91ZrO ₂ 9Y ₂ O _{3 is} formed on the cathode surface from manganite-lanthanum-strontium (molar percentages are indicated). The film thickness depends on the number of carriage passes with a carboxylate dosing device. The growth rate of the thickness of the electrolyte film is 25 microns per hour. After applying the electrolyte, the tube is subjected to heat treatment at a temperature of 1100 ^o C. The cubic structure of the deposited material of the film electrolyte is confirmed by measurements on an x-ray diffractometer. Electrochemical measurements showed that the transport number of oxygen ions in the manufactured electrolyte is almost equal to unity.

 Example 10. One of the variants of the method of manufacturing a film electrolyte according to example 6 is as follows: stabilized zirconia powder having the composition shown in Table 5 (pos. 1) is added to the material applied to the surface of the cathode tube in an amount of 1.5 wt. .%. The fractional composition of the added powder is shown in Fig. 96 96% of its particles have a diameter of less than 2 microns. The electrolyte deposition technology is similar to that used in example 6, but the growth rate of the thickness of the electrolyte layer increased and amounted to approximately 30 - 40 microns per hour. A fragment of an electrolyte layer 30.7 μm thick at the porous cathode is shown in the photograph of FIG. 9.

 Example 11. The manufacture of Ba-Ce-Gd electrolyte on a porous electrode.

A mixture of carboxylates with a composition of Ba, Ce, and Gd, corresponding to Table 5 (item 3), was made as in the previous examples. On a substrate, the temperature of which is maintained at 380 ^o C, which is a porous plate of chromite-lanthanum-strontium, a mixture of carboxylates is sprayed in the form of a gas-droplet emulsion. Upon decomposition of carboxylates, a gas-tight electrolyte film with proton conductivity is formed. The growth rate of the film thickness is 20 μm per hour.

 A preferred method of manufacturing a cermet fuel electrode.

 The manufacture of a cermet fuel electrode with the achievement of the previously mentioned technical result is solved by the fact that in the known method of manufacturing a cermet fuel electrode of a high-temperature fuel cell, comprising forming on a solid electrolyte in contact with an internal air electrode, a cermet electrode layer consisting of a coarse dispersed electron-conducting material selected from the group of metallic nickel and / or cobalt, a coarsely dispersed ion-conducting material based on d carbonated zirconia and / or doped cerium oxide and the subsequent formation on the coarse-dispersed layer of a separate finely divided electrically conductive porous multiphase layer consisting of a metal material selected from the group of nickel and / or cobalt, ion-conductive doped material based on cerium oxide, by applying and subsequent heating the mixture -pastes consisting of the above-mentioned finely dispersed components with a binder, a cermet fuel electrode is made by simultaneously forming by coarse and finely dispersed components of the porous multiphase layer by applying a paste mixture to an electrolyte in contact with the internal air electrode.

Example 12. For the manufacture of cermet fuel electrode, a mixture of carboxylates is prepared - Ni [O ₂ CC (CH ₃ ) ₂ - (CH ₂ ) _n -CH ₃ ] ₂ , where Ni is 60 g / kg, with electrolyte powder (ZrO ₂ ) _{0, 91} (Y ₂ O ₃ ) _0.09 (N 1 table 5) with the ratio (T / W) = 1/3. Nickel powder is added to this mixture at a ratio of (T _YSZ / T _Ni ) = 1 / 1.1 and is processed in a planetary mill. The mixture is applied to the surface of the electrolyte by a coloring method. Next, the element is placed in a vacuum chamber and maintained at a temperature of 350 ^o C and a residual pressure of 10 mm RT.article. for three hours. In this case, nickel carboxylate, which is part of the mixture, decomposes with the formation of metallic nickel, which binds the particles of electrolyte powder and previously mixed nickel powder with a single conductive framework. Next, the finished element is heat treated in an oven at a temperature of 1100 ^o C.

Example 13. For the manufacture of a highly porous cermet anode, on which partial reforming of the fuel is possible, a paste mixture is prepared by mixing powders: nickel, the particles of which have a regular spherical shape (Fig. 11a), doped zirconia, the particles of which have a fibrous structure (Fig. 11b), a fine powder of doped cerium oxide (Fig. 10) with the liquid phase of dimethylbutylacetic cobalt — Co [O ₂ CC (CH ₃ ) ₂ - (CH ₂ ) ₃ -CH ₃ ] ₂ , which during the heat treatment forms an electrically conductive porous multiphase layer oh, fastening together coarse and finely dispersed phases that form the cermet of the fuel electrode.

 The concentration of cobalt in the liquid phase of the carboxylate is 56 g / kg. The weight ratio of nickel metal powder to the total number of ion-conducting powders is 1.1 / 1.0. The ratio of solid to liquid phases in the manufactured paste is in the range of 1/3 - 5/7 mass. The coarse particles of nickel powder have a diameter of 10 to 15 μm, and the coarse powder of the YSZ electrolyte has a filiform shape, where the ratio of the particle length to its diameter is at least 10, with a diameter of 5 to 10 microns.

 The finely divided doped cerium oxide powder contains 90% of particles smaller than 1.0 microns in size.

Application of the paste mixture is carried out by coloring in air at room temperature and atmospheric pressure. The semi-element coated with the crude mixture-paste is subjected to heat treatment in vacuum at a temperature of 350 ^o C and a residual pressure of 10 mm Hg

 A preferred embodiment of the invention for the manufacture of an electrical insulating layer.

 The last component in VTTE is an electrical insulating layer between the current passage and the anode on the surface of the electrolyte. Its need, as noted above, is due to the prevention of spurious current bonds between the electrodes and the elimination of the triple point effect - fuel gas / electrolyte / cathode in the places where the current passage leads.

 Depending on the design of the VTTE, planar or tubular, the conditions and methods for applying the electrical insulating layer differ. For a planar design, a method of applying from a gas-droplet emulsion with masking of neighboring areas is more acceptable, while for a tubular one, a staining method. In this regard, the preparation of the starting materials for applying the insulating layer is different, although it ultimately leads to an insulating coating of the same chemical composition with the same functional properties.

Example 14. For the manufacture of an insulating layer by the method of coloring, a dispersion is used consisting of 30% of the powder material and 70% of the liquid phase. The powder material is magnesia spinel of the composition MgAl ₂ O ₄ with 15% addition of 9YSZ powder, and the liquid phase is a mixture of aluminum and Mg carboxylates, where the organic part of the carboxylates is represented by dimethylbutylacetic acid. The weight ratio between aluminum and magnesium in the carboxylate mixture is designed to form a compound corresponding to MgAl ₂ O ₄ when they are calcined. The content of Mg and Al in carboxylates is presented in Table 1. The dispersion is applied by coloring on a surface heated not higher than 530 ^o C.

Example 15. A method of manufacturing an insulating layer by the method of applying from a gas-drop emulsion is implemented as follows. The organometallic salt of Al and Mg with the composition Mg [Al (Alc) ₄ ] ₂ is mixed with the carboxylates Zr and Y, where the organic part is represented by dimethylbutylacetic acid. Zirconium and yttrium carboxylates are added in an amount sufficient to form 5-15% stabilized zirconium yttrium in magnesia spinel after pyrolysis of the mixture on a heated electrically insulated surface. Application is made in the form of a strip with a width of 2 - 3 mm. The temperature of the electrically insulated surface during application is maintained at 450 ^o C. As a result, an electrically insulating layer with a thickness of 12-15 microns is formed, having a composition corresponding to the chemical formula (MgAl ₂ O ₄ ) _1-n ((ZrO ₂ ) _0.91 (Y ₂ O ₃ ) _0.09 ) _n , where n is 5 - 15 wt.%.

 Industrial applicability. A method of manufacturing a single VTTE and its components: cathode, electrolyte, anode, current passage, interface and insulating layers can be widely used in the technology of manufacturing single VTTE and its components.

 This group of inventions offers an integrated approach to the manufacture of VTTE and its components in the form of a single technological process, using a significantly smaller list of materials, substances and reagents. The same chemical compounds of metals with organic reagents of the same class, prepared in accordance with this group of inventions, are used in the manufacture of all components of VTTE, which also allowed the use of almost one device for the formation of all components within a single technological process.

 As a result, the cost of a single VTTE, and, consequently, the entire product as a whole, is significantly reduced.

Claims (55)

1. A method of manufacturing a high-temperature fuel cell, including the manufacture of a cathode, deposition of an electrolyte and anode, followed by heat treatment of the entire structure of a high-temperature fuel cell, characterized in that after the cathode is fabricated, an interface layer, current passage, an electrolyte based on doped cerium oxide, an electrolyte based on doped oxide are applied zirconium, then the anode and the electrical insulating layer, using one device, and for the manufacture of all applied mating and sintering components s high-temperature fuel cell prepared organometallic complex characterized by the general formula
[(CH ₃ - CH ₂ ) _n - C (CH ₃ ) ₂ - CO ₂ ] _m Me ^{+ m} ,
n = 1 - 7,
m is the valency of the metal,
Me - Mg, Ca, Sr, Ba, Al, Sc, Y, In, La and lanthanides, Ti, Zr, Hf, Cr, Mn, Fe, Co, Ni, Cu, included in the form of metals or their oxides in the composition of materials used to form the cathode, anode, current passage, electrolyte, interface and electrical insulating layers.  2. The method according to claim 1, characterized in that in the manufacture of the cathode organometallic complexes corresponding to the metal component are used as a binder for mixing the moldable mass of the cathode.  3. The method according to claim 1, characterized in that in the manufacturing process of the current passage, electrolyte, interface and insulating layers, organometallic complexes corresponding to the metal component are used as the liquid phase of the organic carriers of finely divided solid phases of the corresponding powder materials for the manufacture of current leads, electrolytes, interface and electrical insulating layers.  4. The method according to claim 1, characterized in that in the process of manufacturing the anode, the organometallic complex is used as the liquid phase in the preparation of the paste mixture, comprising a coarse and fine dispersion of ionic and electronically conductive corresponding powder materials constituting the cermet of the anode.  5. The method according to claim 1 or 3, characterized in that in the manufacturing process of a thin-film solid oxide electrolyte, interface and electrical insulating layers, the organometallic complex of the corresponding composition is used directly in the form of a liquid phase. 6. A method of manufacturing a supporting ceramic cathode of a high-temperature fuel cell, comprising synthesizing an electrode material powder - doped lanthanum manganite, preparing a moldable mixture with an organic binder component, forming a carrier base followed by sintering, characterized in that the synthesis of the electrode material powder is carried out by the precipitation of carbonates from carbon their nitrate solutions followed by their synthesizing roasting, and as an organic binder component for synthesized of the powder of the electrode material, carboxylates of the chemical elements La, Mn, Ni, Cr, Co doped from the group of alkaline-earth elements are used, and the formation of the supporting ceramic cathode is carried out by isostatic pressing followed by sintering at a temperature not exceeding 1100 - 1380 ^o C. 7. The method according to claim 6, characterized in that, in order to achieve non-shrinking sintering of the cathodes from a powder of electrode material characterized by the formula La _x A _1-x MnO ₃ , where A is either Mg, or Ca, or Sr, or Ba, or their mixture, 0.6 ≤ x ≤ 1.0, synthesizing the firing of co-precipitated carbonates of these elements is carried out at a temperature not exceeding 1380 ^o C. 8. The method according to claim 6, characterized in that for the preparation of an organic binder component based on metal carboxylates, acids with the general formula C _n H _{2n + 1} O _{2 are used} , where n = C ₆ is C ₁₂ .  9. The method according to claim 6, characterized in that the total concentration of metals in the carboxylates is in the range of 20 to 360 g / kg  10. The method according to claim 6, characterized in that the mass of the organic binder component is 3 to 15 wt.% With respect to the moldable mass. 11. The method according to claim 6, characterized in that the electrode material powder synthesized according to claim 7 is closed with an organic binder component containing Mn, La, or Co, La, or Cr, La, or Ni, La, doped with elements from groups of alkaline-earth elements forming, after decomposition of a compound of the composition La _y Sr _1-y MnO ₃ , or La _y Sr _1-y CoO ₃ , or La _y Sr _1-y CrO ₃ , or La _y Sr _1-y NiO ₃ , where 0.6 ≤ y ≤ 1.0. 12. A method of manufacturing a solid oxide electrolyte of a high-temperature fuel cell, which consists in preparing the initial organometallic compound, heating the ceramic electrode to a predetermined temperature, applying the prepared organometallic compound to the electrode surface and subsequent heat treatment of the electrode with the formed electrolyte, characterized in that the organometallic compound for the manufacture of solid oxide the electrolyte is synthesized using the reaction Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _A + Me ^{+ A} (OC _m H _{2m + 1} ) _A

Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _X (OC _m H _{2m + 1} ) _AX ;
with the formation of a mixture of metal carboxylates, or a mixture of metal alkoxides, or a mixture of metal carboxylates and alkoxides of metals, characterized by the General formula
Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _X (OC _m H _{2m + 1} ) _AX ,
where Me is any of the metals included in the functional component of a high-temperature fuel cell;
A is the valency of a given chemical element (metal);
X is the coefficient determined from the inequality 0 <X <A;
n is 1 to 7;
m = 2 - 8. 13. The method according to p. 12, characterized in that the mixing of the starting components in the process of preparing the organometallic compounds is carried out at a temperature of (80 - 100) ^o C. 14. The method according to p. 12, characterized in that for the preparation of metal carboxylates, the synthesis of metal carboxylates, characterized by the General formula
Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _A ,
carried out by liquid extraction and / or solid-phase extraction of the corresponding metals (Me ^{+ A} ) from aqueous solutions of their salts and / or their suspensions in mineral acids. 15. The method according to p. 12, characterized in that for the preparation of zirconium alcoholate, the synthesis of zirconium alcohol Zr (OC _m H _{2m + 1} ) _{4 is} carried out in the process of interaction of the mineral salt of zirconium with alcohol and calcium metal when they are boiled. 16. The method according to p. 12, characterized in that the organometallic compound with zirconium prepared in accordance with p. 14 or 15 of the claims and modified with at least one of the elements Mg, Ca, Sc, Y, Ce and / or lanthanides, applied to the surface of the supporting cathode by rolling, dyeing or spraying a gas-liquid emulsion, scanning the agent applying the prepared composition over the surface of the cathode at a temperature of a heated electrode (400 - 550) ^o C.  17. The method according to p. 16, characterized in that the deposition of the organometallic compound on the heated surface of the ceramic electrode is carried out with a growth rate of the film thickness (10-40) μm / h. 18. The method according to p. 12 or 14, characterized in that the organometallic compound modified with at least one of the elements Mg, Ca, Sc, Y and / or lanthanides is applied to the surface of the electrode, heated to a temperature not exceeding 400 - 550 ^o C. 19. The method according to p. 12 or 15 based on zirconium dioxide, characterized in that the organometallic compound with zirconium, modified with at least one of the elements Mg, Ca, Sc, Y and / or lanthanides, is applied to the surface of the electrode heated to a temperature (300 - 400 ^o C.  20. The method according to p. 12, or 14, or 15, or 18, or 19, characterized in that to increase the speed of applying the electrolyte film to the applied composition, a powder of modified zirconia is added before application.  21. The method according to p. 20, characterized in that the powder of the modified zirconia dioxide comprises 95% of particles with a size of less than 2 microns, and its amount in the mixture is (0.1 - 2.0) wt.%.  22. The method according to p. 12, characterized in that the process of applying the organometallic compound to the heated surface of the ceramic electrode is carried out in an inert medium. 23. The method according to p. 12 or 14, characterized in that to obtain a proton electrolyte prepare a mixture of carboxylates, characterized by the chemical formula
SrCe _0.85 Gd _0.15 (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) ₆ or BaCe _0.85 Gd _0.15 (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) ₆ ,
where n = 2 - 3, is applied to the electrode surface, heated to a temperature not exceeding 470 ^o C, decomposing under the influence of temperature with the formation of a proton electrolyte film of the composition SrCe _0.85 Gd _0.15 O ₃ or BaCe _0.85 Gd _0.15 O ₃ . 24. The method according to p. 12, characterized in that after applying the prepared organometallic compound to the heated electrode surface, the resulting semi-element is subjected to heat treatment at a temperature not exceeding 1250 ^o C.  25. A method of manufacturing a current passage of a high-temperature fuel cell, comprising synthesizing an electron-conducting material powder based on doped lanthanum chromite, manufacturing an ultrafine mixture from synthesized powder in organic media and applying it to a carrier cathode, followed by heat treatment, characterized in that a fine dispersion is produced by grinding the synthesized powder electron-conducting material of doped lanthanum chromite to an ultrafine state in a liquid medium of a mixture of organometallic complexes of chromium, lanthanum and doping elements, after which the current passage film is made by repeatedly applying a fine dispersion to the surface of the supporting cathode, heated to the temperature of formation of a mixture of organometallic complexes of chromium, lanthanum and doping elements of a gas-tight film of doped lanthanum chromite of the same composition as the finely divided powder synthesized separately. 26. The method according to p. 25, characterized in that for the manufacture of a carrier of a fine dispersion of powdered doped lanthanum chromite synthesize chromium carboxylates, lanthanum and doping elements, characterized by the formula
Me ^{+ M} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _m ,
where Me is Cr, La, Sr, and / or Ca, and / or Mg;
m is the valency of the metal;
n = 1 - 7.  27. The method according to p. 25, characterized in that the ratio of solid to liquid phases in the manufactured fine dispersion is in the range (1/100 - 15/100) of the mass.  28. The method according A.25, characterized in that the concentration of Cr, La, Sr, Mg, Ca in the mixture of carboxylates is in the range from 20 to 110 g / kg  29. The method according A.25, characterized in that the application of the current passage is carried out by painting at atmospheric pressure in air.  30. The method according A.25, characterized in that the application of the current passage is carried out by spraying the prepared mixture of carboxylates in an inert medium.  31. The method according to p. 25, characterized in that the growth rate of the thickness of the gas-tight film of the current passage on the surface of the supporting porous cathode is at least 60 μm / h 32. The method according A.25, characterized in that the temperature of the formation of the current passage from the doped lanthanum chromite on the surface of the supporting cathode does not exceed 600 ^o C. 33. A method of manufacturing an interface layer, including the synthesis of an organometallic complex, its deposition on a heated substrate, characterized in that a compound characterized by the general formula is used as an organometallic complex
Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _AX (OC _m H _{2m + 1} ) _X ,
where Me are metals selected from the group: Cr, Mn, Co, Ni, Cu, Y, Zr, La and lanthanides, Mg, Ca, Sr, Ba;
A is the valency of a given chemical element (metal);
X is the coefficient determined from the inequality 0 <X <A;
n is 1 to 7;
m = 2 - 8. 34. The method according to p, characterized in that for the manufacture of a gas-tight film of the interface layer using a mixture of compounds characterized by the General formula
Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _AX (OC _m H _{2m + 1} ) _X ,
where X = 0;
Me - metals selected from the group: Mg, Ca, Sr, Ba, Ce, Pr, Sm, Gd, Er.  35. The method according to p, characterized in that the total metal content in the mixture of compounds is not more than 20 g / kg 36. The method according to p. 33, characterized in that the deposition is carried out on a substrate heated to a temperature not exceeding 530 ^o C in an atmosphere of air with the formation of a gas-tight film of the interface layer with a thickness of not more than 0.6 μm based on doped lanthanum chromite that activates the electrode reaction . 37. The method according to p, characterized in that for the manufacture of a gas-tight film of the anti-diffusion interface layer using a mixture of compounds characterized by the General formula
Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _AX (OC _m H _{2m + 1} ) _X ,
where X = 0;
Me - metals selected from the group: Ce, and doping elements Sm, Gd;
n = 1, 2.  38. The method according to clause 37, wherein the total metal content in the mixture of compounds is not more than 20 g / kg 39. The method according to clause 37, wherein the application of the mixture is carried out on a substrate heated to a temperature of not higher than 380 ^o C in an inert gas atmosphere with the formation of a gas-tight, anti-diffusion film of the interface layer with a thickness of not more than 10 microns based on doped cerium oxide. 40. The method according to p. 33, characterized in that for the manufacture of the interface layer that protects the previous layer from the reducing gas medium, a mixture of compounds characterized by the general formula
Me ^{+ A} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _AX (OC _m H _{2m + 1} ) _X ,
where Me are metals selected from the group: Zr, Y, La and lanthanides,
A is the valency of a given chemical element (metal);
X - can take the values 1, 2, 3, ... A.  41. The method according to p, characterized in that the total content of zirconium and doping components in the mixture is not more than 50 g / kg 42. The method according to p. 40, characterized in that the application of the mixture is carried out by coloring the substrate, heated to a temperature of not higher than 430 ^o C in an inert gas atmosphere with the formation of a protective interface layer, a thickness of not more than 5 microns, based on doped zirconia. 43. The method according to § 42, characterized in that as the inert gas atmosphere use either Ar, or N ₂ , or CO ₂ .  44. A method of manufacturing a cermet fuel electrode of a high-temperature fuel cell, comprising forming, on a solid electrolyte in contact with an internal air electrode, a cermet electrode layer consisting of a coarse dispersed electron-conducting material selected from the group of metallic nickel and / or cobalt, a coarse ion-conducting material based on doped zirconia and / or doped cerium oxide, and the subsequent formation on a coarse-dispersed layer of a separate tone a dispersed electrically conductive porous multiphase layer consisting of a metal material selected from the group of nickel and / or cobalt, an ion-conductive doped material based on cerium oxide, by applying and subsequent heating a paste mixture consisting of said finely dispersed components with a binder, characterized in that the cermet the fuel electrode is produced by the simultaneous formation of coarse and finely dispersed components of the porous multiphase layer by applying a mixture of paste to ktrolit in contact with an inner air electrode. 45. The method according to item 44, wherein the paste mixture is prepared by mixing powders of coarse electrically conductive material selected from the group of metallic nickel and / or cobalt, coarsely dispersed ion-conducting material based on doped zirconia and / or doped cerium oxide, finely dispersed ion-conducting material based on doped cerium oxide and the liquid phase of nickel and / or cobalt carboxylates, characterized by the general formula
Me ^{+ m} (O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _m ,
where Me is Ni and / or Co,
m is the valency of the metal,
n = 1 - 7,
which during heat treatment forms an electrically conductive porous multiphase layer, fastening together coarse and finely dispersed phases that form the cermet of the fuel electrode. 46. The method according to item 44, wherein the ratio of phases solid to liquid in the manufactured paste is in the range of - (1/3 ^o C 5/7) mass.  47. The method according to item 44, wherein the concentration of Nickel and / or cobalt in liquid carboxylates is in the range from 20 to 70 g / kg of carboxylate.  48. The method according to item 44, wherein the Nickel and / or cobalt powder is added in relation to the amount of metal powder to the amount of electrolyte powder as 1.1: 1.0.  49. The method according to item 44, wherein the coarse particles of Nickel and / or cobalt powder have a regular spherical structure with a diameter of from 10 to 15 microns.  50. The method according to item 44, wherein the synthesized coarse electrolyte powder has a threadlike shape, and the ratio of the particle length to its diameter is not less than 10, with a particle diameter of 5 to 10 microns.  51. The method according to paragraph 44, wherein the fine powder of doped cerium oxide contains at least 90% of particles with a diameter of less than 1.0 microns.  52. The method according to item 44, wherein the application of the mixture-paste is carried out by coloring in air at room temperature and atmospheric pressure. 53. The method according to item 44, wherein the semi-element coated with a crude mixture of paste is subjected to heat treatment in vacuum at a temperature of not higher than 400 ^o C and a residual pressure of not more than 0.1 ATM. 54. A method of manufacturing an insulating layer of VTTE, comprising preparing a mixture of components based on magnesia spinel, characterized in that the second component in the prepared applied mixture uses a mixture of organometallic complexes with the general formula
Me ^{+ A} [(O ₂ C - C (CH ₃ ) ₂ - (CH ₂ ) _n - CH ₃ ) _1-X (OC _m H _{2m + 1} ) _X ] A,
where n = 1 to 7;
m is 2-8;
Me — Mg, Al, Zr, Y, Ca, La, and lanthanides;
A is the valency of the metal;
x - can take values from 0 to 1. 55. The method according to item 54, wherein the deposition of an electrically insulating layer on the surface intended for insulation is carried out by heating the manufactured high-temperature fuel cell to a temperature of not higher than 600 ^o C.

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