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The high-temperature cell element electrochemical devices

The high-temperature cell element electrochemical devices
IPC classes for russian patent The high-temperature cell element electrochemical devices (RU 2178561):
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(57) Abstract:

Usage: high temperature electrochemistry in the construction of fuel cells. The inventive cell high-temperature electrochemical device comprises a tubular element of a solid electrolyte with a cathode and an anode, a gas-feeding tube installed inside the tubular element, dispersed conductive material placed in the cavity between the gas-feeding tube and the inner surface of the tubular element, the gas-permeable ring, which is made in the form of polution with providersmichelin walls, the surface of polution made with perforation, with an increasing gradient of gas permeability in the direction of the inner surface of the tubular element, the ring is additionally installed in the layer of dispersed material, rings and a gas-feeding tube made of a metal material. Technical result - increase the reliability of the cell. 2 Il.

The invention relates to high-temperature electrochemistry, and more particularly to structures gaseous diffusion cells are electrochemical devices with solid electrolyte, and can be used in the construction of topographytemprate electrochemical device with a solid electrolyte, protected but. C. N 1748508, G 01 N 27/50 from 16.01.90, the Electrode contains a tube of solid electrolyte with the anode and the cathode layer of the electrode active substance and a gas-feeding tube. As electrode-active substances are used dispersed material dendritic structure.

A disadvantage of the known device is that the potential is removed from such electrode is small, due to small working surface of the tube. Sensor design uneconomical because it requires use of the transmission elements of an electrical signal, made from platinum, the scope of application of the sensor is limited potentiometric registration oxygen concentration.

Known for the design of the probe with the solid electrolyte described in the application Germany N 3709196, G 01 N 27/50/98, the Probe contains a tube of solid electrolyte, which is equipped with a gas-feeding tube, in the space between the tube and the inner surface of the tube is placed grains dispersed material with electronic or mixed conductivity, which is limited to the filling of the insulating material. In the layer of fill metal is a wire electrode, and the outer surface of the tubes is similar Alamosa to the technical essence and selected as a prototype.

A disadvantage of the known device is that when the cell cyclic thermal stress lead to the creation of internal stresses in the material of the tubular element, granular backfill. These stresses caused by the difference in coefficients of linear thermal expansion (cltr) materials of various parts of the device. The presence of internal stresses can lead to cracking and grinding of granules filling, integrity of the tubular element. In addition, in the case of an emergency stop of the operation of the cell, while stopping the supply of gas fuel may get into the cavity of the tubular element oxidant is air, which will lead to oxidation of the anode and Nickel pellets, Nickel - cermet grade. The oxidation products have a volume much greater than the volume of particles of metallic Nickel. The increase in the volume of backfill and anode will lead to the creation of internal stresses in the material of the tubular element.

The claimed invention solves the problem of improving reliability by maintaining the integrity of the cell during thermal Cycling loads and emergency stops.

To solve the problem in the cell high-temperature electrochemical mouth of the pipe, installed inside the tubular element, dispersed conductive material placed in the cavity between the gas-feeding tube and the inner surface of the tubular element, the gas-permeable ring according to the invention the ring is made in the form of polution with providersmichelin walls, the surface of polution made with perforation, with an increasing gradient of gas permeability in the direction of the inner surface of the tubular element, the ring is additionally installed in the layer of dispersed material, rings and a gas-feeding tube made of a metal material. The possibility of implementation of the tasks due to the fact that provideproperty wall polution allow you to remove the internal stresses on the wall of the tubular element generated during thermal Cycling loads, due to the deformation of the thin wall and a half. In addition, a cavity formed between the outer surface of the half, the walls of the gas-feeding tube and the tubular element is not filled dispersed material and, on the one hand, create an additional volume, which will allow you to compensate for volumetric changes in particulate material and the anode in the case of oxidation in case of emergency situationto design. In addition, create an area of active interaction of the gas stream with three-phase boundary by increasing the permeability of the rings in the area of the contact surface of the half with a cavity adjacent to the tubular element, where the basic electrochemical processes.

The presence of the distinctive features of the prototype allows to make a conclusion on the conformity of the proposed technical solution the criterion of "novelty".

In the search process not identified technical solutions containing signs, similar to the distinctive features of the proposed solutions, which allows to make a conclusion on compliance with a criterion of "inventive step".

The cell design is illustrated in the drawings, is shown in Fig. 1 and 2.

Fig. 1 - General view of the cell.

Fig. 2 - section a-A.

The cell is a 1 tube of solid electrolyte, the anode 2, located on the inner surface of the tube in the form of pripechnogo layer of Nickel-cermet grade. The cathode 3 is placed on the outer surface of the tube in the form of pripechnogo layer of manganite lanthanum-strontium. In the cavity of the tube is a gas-feeding pipe 4 from vysokoskorostnogo metal material is Jena dispersed material 5 of the Nickel-cermet grade. In the layer of material placed rings 6, which are made in the form of a half with the holes 7. Perforation 7 is designed so as to form an increasing gradient of gas permeability in the direction from the wall of the gas-feeding tube to the surface of the tubular element. Ring 6 is installed as limiting the filling of the dispersed material, and the layer of filling. Ring 6 is installed assasino in the cavity of the tube 1. Rings form a cavity 8 between the outer surface of the half and the walls of the gas-feeding tube and the cavity 9 between the surface of the half and the wall of the tubular element. Power collection 10 located outside of the tube, passes the current from the cathode 3 to the current terminals 11.

The device operates as follows. The fuel gas is fed to the tube 4, in the bottom part of the tube 1, the gas passes through the ring 6 and the dispersed material 5 to the anode 2. On three-phase boundary of gas - material of the anode 2 is the solid electrolyte 1" is the electrochemical interaction of the fuel with the oxygen ions flowing through the electrolyte with 1 cathode 3. When interacting generation of free electrons and water vapor. Water is removed through the dispersed material Nickel-cermet grade, and electrons through the ring 6 and the conductive material filling 5 go to e the load. Through the load circuit, the electrons arrive at the cathode the current terminals. On three-phase boundary of gas - oxidizer to the cathode 3 is the solid electrolyte 1" is the electrochemical interaction of the electron with a molecule of oxygen from the carrier gas, with the formation of oxygen ions that are moving through the electrolyte, completing the circuit.

Because cltr Nickel and Zirconia, sintered in the Nickel-cermet grade are significantly different, when heated to operating temperatures of 900 - 1000oC in the particles of the Nickel-cermet grade have significant internal stresses that can cause failure of the dispersed material and the seal. Thermal Cycling loads occur due to starts and stops of the cell. When dense packing of granules volumetric changes due to differences cltr give rise to stresses in the walls of the tubular element. Available cavities 8 and 9 allows the volume to compensate for these changes and to reduce tension in the walls of the tubular element. In the case of an emergency, when there is a hit of a gas-oxidizing agent into the cavity of the tubular element is in the process of oxidation of Nickel from the backfill layer and the anode. The resulting Nickel oxide has a volume significantly Ave is her 8 and 9 allows to avoid increasing pressure on the wall of the tubular element above the critical, leads to destruction. The increase in the permeability of the surface of the half in the region adjacent to the cavity 9, facilitates the efficient supply of fuel to the surface of the tubular element, free from the backfill. There are electrochemical processes on the surface of the anode, there is power collection ring surface closely adjacent to the surface of the anode. Calculations show that the use of 30 rings in the layer of backfill with an inner diameter of the tubular element 10 mm, length 210 mm, the outer diameter gas supplying tube 4 mm allows you to get the free volume of 640 mm3and during emergency situations, the maximum volume change can be 640 mm3.

In the process of working out the design of the cell at the Institute tested the cell, which is the tube from the electrolyte on the basis of stabilized yttria Zirconia dimensions: diameter 10 mm, length 210 mm from the cathode on the outer surface of manganite lanthanum-strontium thickness of 0.25 mm and an anode on the inner surface of the Nickel-cermet grade with a thickness of 0.06 mm In vitro installed a gas-feeding tube made of Nickel, which missed the fuel is hydrogen. The gas passed through the layer of dispersed Nikiforovna ring of Nickel in the form of a half. Number of rings - 30 PCs power collection from the cathode was made by means of wire rings made of platinum. The contacts were connected by welding with Nickel cold end. The maximum power of the cell is 6.5 watts.

The high-temperature cell element electrochemical device containing the tubular element of the solid electrolyte with the cathode and the anode, a gas-feeding tube installed inside the tubular element, dispersed conductive material placed in the cavity between the gas-feeding tube and the inner surface of the tubular element, and a gas-permeable ring, limiting the filling of the dispersed material, characterized in that the ring is made in the form of polution with providersmichelin walls, the surface of polution made with perforation, with an increasing gradient of gas permeability in the direction from the wall gazoprovoda tube to the surface of the tubular element, the ring is additionally installed in the layer of dispersed material, and rings and a gas-feeding tube made of a metal material.

 

 

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