JP2006258623A - Oxygen pump element and oxygen supply device using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxygen pump element capable of being brought to a high voltage and small current state to be operated. <P>SOLUTION: A metal foil member 12 coated with an insulating film has a plurality of openings and a plurality of oxygen ion conductive solid electrolytes 7 are arranged to the openings so as to seal the openings by gas while positive and negative electrode films are formed on both surfaces of the solid electrolytes 7 and a plurality of the solid electrolytes 7 are arranged so that the positive and negative electrode films serve as a series circuit electrically. By this arrangement, since a plurality of the solid electrolytes 7 are constituted so as to electrically become the series circuit, the voltage applied to the solid electrolytes can be accumulated and the oxygen pump element is brought to a high voltage and small current state to be operated. Further, the solid electrolytes 7 are arranged on the metal foil member 12 and have a sufficient flexibility even with respect to a heat shock and heat strain. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an oxygen pump element using an oxygen ion conductive solid electrolyte and an oxygen supply device using the same.

  Conventionally, this type of oxygen pump, when using a plurality of oxygen ion conductive substrates at the same time, electrically connects the electrode films on the same surface side with lead wires or the like, and applies a power supply voltage in parallel. (For example, see Patent Document 1).

As shown in FIGS. 8 and 9, a large number of oxygen ion conductive substrates 1 are fixed to the support member 2. Lead wires 4 are drawn out from the peripheral portions of the respective electrode films 3 and gathered, and are connected to the wirings at the same potential. A lead wire 5 is drawn out from the wiring and connected to one pole of the power source. A lead wire 6 similarly drawn from the back surface is connected to the other pole of the power source.
Japanese National Patent Publication No. 8-527485

  However, in the conventional configuration, since a plurality of oxygen ion conductive substrates 1 are connected in parallel, a large current flows through the lead wire in which the lead wires are gathered. Therefore, there is a problem that it is necessary to use a sufficiently thick lead wire or a special lead wire having a small electric resistance. Further, for example, when considering actual use at home, a current of several tens of amperes is more complicated than a voltage of several tens of volts, resulting in a problem in that the configuration of the power supply circuit is complicated and the cost is high.

  The present invention solves the above-described conventional problems, and an object thereof is to provide an oxygen pump element that can be operated with a high voltage and a small current, and an oxygen supply device using the oxygen pump element.

  In order to solve the above-described conventional problems, the oxygen pump element of the present invention and the oxygen supply device using the oxygen pump element include a metal foil member covered with an insulating film having a plurality of openings, and oxygen ion conduction in the openings. A plurality of solid electrolytes that are gas-sealed, and a positive electrode film and a negative electrode film are formed on both surfaces of the solid electrolyte, and the positive electrode film and the negative electrode film are electrically connected in series in the plurality of solid electrolytes. An oxygen pump element is configured so as to form a circuit, and this is used as an oxygen supply device.

  As a result, a voltage applied to the solid electrolyte can be accumulated by constructing a metal foil member coated with an insulating film so that a plurality of solid electrolytes are electrically connected in series, thereby increasing the oxygen pump element. It is possible to operate with a reduced voltage current. Further, since the solid electrolyte is disposed on the metal foil member, it has sufficient flexibility against thermal shock and thermal strain.

  The oxygen pump element of the present invention and the oxygen supply device using the oxygen pump element can accumulate voltages applied to the solid electrolyte, and can be operated with a general-purpose power source with a high voltage and a small current.

  According to a first aspect of the present invention, a metal foil member coated with an insulating film has a plurality of openings, and a plurality of oxygen ion conductive solid electrolytes are gas-sealed in the openings and disposed on both sides of the solid electrolyte. A positive electrode film and a negative electrode film are formed, and a plurality of solid electrolytes are formed as an insulating film by forming an oxygen pump element in which the positive electrode film and the negative electrode film are electrically connected in series. By configuring multiple solid electrolytes to be electrically connected in series on the coated metal foil member, the voltage applied to the solid electrolyte can be accumulated, and the oxygen pump element operates with a high voltage and a small current. It becomes possible to make it. Further, since the solid electrolyte is disposed on the metal foil member, it has sufficient flexibility against thermal shock and thermal strain.

  According to a second aspect of the invention, in particular, in the first aspect of the invention, one solid electrolyte is arranged in a pair structure in which a positive electrode film and a negative electrode film are divided into a plurality of parts to form a capacitor, and the positive electrode film In addition, since the negative electrode film is configured to be electrically connected in series, the voltage applied to one solid electrolyte can be accumulated by dividing the positive electrode film and the negative electrode film. The current value to the whole oxygen pump element can be kept low with a small number of solid electrolytes.

  According to a third invention, in particular, in the first or the second invention, the gas seal includes at least one positive electrode film or negative electrode in which the periphery of the opening of the metal foil member and the outer periphery of the solid electrolyte are joined by a conductive film. Since the electrode film is electrically connected to the conductive film, gas sealing can be performed with the conductive film, and the electrode film can be used as a lead extraction portion from the positive electrode film or the negative electrode film. Gives you more freedom. In addition, the conductive film has sufficient flexibility against large thermal shocks and thermal strains generated in the solid electrolyte.

  In particular, in a fourth invention, in any one of the first to third inventions, the conductive film which is a gas seal between the metal foil member and the solid electrolyte, and at least one positive electrode film or negative electrode on the solid electrolyte By connecting the lead part to the film and taking out the lead part from the same plane direction with respect to the metal foil member surface, the power supply circuit necessary for oxygen ion conduction can be limited in one direction and the layout configuration of the device can be It can be simplified.

  According to a fifth invention, in particular, in any one of the first to fourth inventions, the positive electrode film and the negative electrode film formed on both surfaces of one solid electrolyte are connected to each other through a through hole provided in the solid electrolyte. By connecting them to form a series circuit, multiple positive electrode films and negative electrode films can be connected to one side at a time by screen printing or other methods, simplifying the manufacturing process for mass production. Can be

  In a sixth aspect of the invention, in particular, in any one of the first to fifth aspects of the invention, a single metal foil member is configured as a partitioning means for partitioning a space where the solid electrolyte is located, thereby providing a plurality of The space portions located on both sides through the solid electrolyte are separated by a single metal foil member, so that sufficient gas sealing performance can be maintained.

  According to a seventh invention, in particular, in any one of the first to sixth inventions, the positive electrode film and the negative electrode film are formed on the first electrode film and the first electrode film that is directly bonded to the solid electrolyte. The first electrode film is a film mainly composed of a composite metal oxide component on a solid electrolyte, and the second electrode film is a film mainly composed of a noble metal component, Since the two-electrode film is made of a highly conductive material, an equal potential could be applied to the electrode portion having a certain area. Moreover, since the first electrode film can enhance the electrode reaction of dissociating and adsorbing oxygen as an intermediate layer between the solid electrolyte and the second electrode film, a good catalytic action for changing from oxygen molecules to oxygen ions can be obtained. Can do.

  The eighth invention is a perovskite-type composite metal oxide mainly comprising lanthanum and gallium because the solid electrolyte is lanthanum gallate in any one of the first to seventh inventions. And oxygen ion conductivity at 400 ° C. or higher. Therefore, since sufficient capability can be obtained by maintaining the operating temperature of the oxygen pump element at a relatively low temperature of about 600 ° C., deterioration of the oxygen pump element can be suppressed even in the long term.

  In the ninth invention, in particular, in the seventh or eighth invention, the composite metal oxide of the first electrode film has a perovskite structure, so that oxygen is dissociated and adsorbed as an intermediate layer between the solid electrolyte and the second electrode film. Therefore, the oxygen ion conductivity as an oxygen pump element can be improved.

  In the tenth invention, in particular, in any one of the third to ninth inventions, the conductive film is mainly composed of a noble metal component, so that it can sufficiently cope with thermal shock and thermal strain generated in the solid electrolyte. Therefore, the solid electrolyte can be prevented from peeling off from the metal foil member.

  In an eleventh aspect of the invention, in particular, in any one of the first to tenth aspects, the metal foil member is a ferritic stainless steel containing aluminum, so that it has excellent characteristics against high-temperature oxidation. , Stable characteristics can be maintained for long-term use at around 800 ° C.

In a twelfth aspect of the invention, in particular, in any one of the first to eleventh aspects of the invention, the insulating film is obtained by being a TiO ₂ film or a ZrO ₂ film formed on the surface of the metal foil member by a liquid phase deposition method. The insulation film can sufficiently cope with the high temperature used in the oxygen pump, and the insulation film is a very thin film, so that the solid electrolyte is peeled off from the metal foil member without impairing the flexibility of the metal foil member. Therefore, it is possible to maintain the insulation necessary for making the solid electrolyte into a series circuit.

  The thirteenth invention, in particular, the oxygen pump element according to any one of the first to twelfth inventions, voltage application means for applying a voltage to the oxygen pump element, and voltage control means for controlling the voltage application means, Heating means for heating the oxygen pump element; temperature control means for detecting the temperature of the oxygen pump element to control the heating means; and heat insulating means for preventing thermal diffusion of the heating means and the oxygen pump element. The oxygen supply device includes a mixing unit that mixes oxygen generated through the oxygen pump element with air to form a mixed gas having a predetermined oxygen concentration, so that the voltage applied to the oxygen pump element is a plurality of solids. Since the electrolyte is configured in a series circuit, a voltage is accumulated, and the oxygen pump element can be operated with a general-purpose power source with a high voltage and a small current. Moreover, since the space part located on both sides via a solid electrolyte is divided by one metal foil member, sufficient gas sealing performance can be maintained. In addition, since the oxygen pump element, the partitioning means, and the heating means can be made a simple structure covered with a heat insulating material, the oxygen pump can be miniaturized and can be easily mounted on a device.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments.

(Embodiment 1)
1 to 3 show an oxygen pump element and an oxygen supply device using the same according to an embodiment of the present invention.

  As shown in FIGS. 1 and 2, in the oxygen pump element according to the present embodiment, the metal foil member 12 covered with an insulating film has a plurality of openings 12a (FIG. 3), and oxygen ions are formed in the openings 12a. A plurality of conductive solid electrolytes 7 are gas-sealed with a conductive film 13, a positive electrode film 8 and a negative electrode film 9 are formed on both surfaces of the solid electrolyte 7, and the plurality of solid electrolytes 7 are the positive electrode films 8 and the negative electrode film 9 are configured to electrically form a series circuit. In the present embodiment, an Au porous positive second electrode film 10 and a negative second electrode film 11 are laminated as the second electrode film on the surfaces of the positive electrode film 8 and the negative electrode film 9.

The solid electrolyte 7 is a sintered body of substitutional type lanthanum gallate (La _0.8 Sr _0.2 Ga _0.8 Mg _0.2 O ₃ ) molded into a flat plate having an arbitrary thickness. As films, the positive electrode film 8 and the negative electrode film 9 are formed so as to exhibit oxygen ion conductivity. Here, description will be made assuming that the solid electrolyte has a size of 15 × 15 mm and a thickness of 100 μm.

For the positive electrode film 8 and the negative electrode film 9, a perovskite complex oxide having conductivity was used. Specifically, a paste prepared by mixing Sm _0.5 Sr _0.5 CoO ₃ with a cellulose-based vehicle as an organic solvent is formed by screen printing to form a printed film, dried, and fired at 1100 ° C. to obtain a film thickness of about 15 μm. An electrode film having porosity was formed.

  Further, the positive second electrode film 10 and the negative second electrode film 11 laminated on the surfaces of the positive electrode film 8 and the negative electrode film 9 are made of Au paste, screen-printed to form a printed film, and after drying, 800 A second electrode film having a thickness of about 3 μm was formed by baking at a temperature of 0 ° C. The positive second electrode film 10 and the negative second electrode film 11 can improve the surface distribution unevenness of the solid electrolyte 7 with respect to the potential when a voltage is applied between the positive electrode film 8 and the negative electrode film 9.

  Here, as shown in FIG. 2, an oxygen pump element in which 36 solid electrolytes 7 are used will be described.

Each solid electrolyte 7 is connected to a metal foil member 12 whose negative electrode film 9 side is covered with a single insulating film. As the metal foil member 12 using Fe-20Cr-5Al, the 12 [mu] m, the surface having an insulating property because TiO ₂ is about 0.2μm covered by a liquid phase precipitation method. The metal foil member 12 is provided with 36 openings 12a and 12 × 12 mm so that the surface of the negative second electrode film 11 of the solid electrolyte 7 is exposed. The negative electrode film 9 side of the outer periphery of the solid electrolyte 7, that is, the negative second electrode film 11 is gas-sealed by a conductive film 13 and bonded to the metal foil member 12. Since the size of the solid electrolyte 7 is 15 × 15 mm and the opening 12 a provided in the metal foil member 12 is 12 × 12 mm, the joint portion formed by the conductive film 13 has a width of 1.5 mm around the solid electrolyte 7. The Au paste was used as the conductive film 13 in the opening 12a of the metal foil member 12, and screen printing was performed twice so that a lead extraction portion could be formed in a part of 16 × 16 mm. Then, 36 solid electrolytes 7 were joined to the metal foil member 12 by drying and firing at 750 ° C.

  The lead extraction portion formed by the conductive film 13 electrically connected to the negative second electrode film 11 of each solid electrolyte 7 and the positive second electrode film 10 side of the adjacent solid electrolyte 7 are connected electrically to each other. It is a series circuit. The connection was made with a gold wire 14 of φ0.1 mm. In FIG. 2, the individual solid electrolytes 7 are numbered (1 to 36) in the order of connection in a series circuit. The lead part 15 finally connected to the positive second electrode film 10 of the first solid electrolyte 7 for the 36 solid electrolytes 7, the negative second electrode film 11 of the 36th solid electrolyte 7, and the electricity The voltage is applied to the entire oxygen pump element from the lead portion 16 connected to the conductive film 13 that is electrically conductive. The lead portions 15 and 16 are taken out from the same plane direction with respect to the surface of the metal foil member 12.

  FIG. 3 shows a configuration of an oxygen supply apparatus using the oxygen pump element.

  The periphery of one metal foil member 12 serving as a space partitioning means for 36 solid electrolytes 7 is fixed to a support 18 with an electrically insulating gas sealant 17. Further, a voltage applying means 19 for applying a voltage to the oxygen pump element and a voltage control means 20 for controlling the voltage applying means 19 are connected to the lead portion 15 and the lead portion 16 through a lead wire. The heater 22 of the heating means 21 that heats the oxygen pump element is disposed opposite to the surface on the negative electrode film side, and the temperature control means 23 having the means 23 a for detecting the temperature of the solid electrolyte 7 sends a signal to the heating means 21. To control the heating means 21.

  As the means 23a for detecting the temperature of the solid electrolyte 7, a temperature sensor or other means may be used. In the case of a sensor, the sensor may be disposed in the vicinity of the solid electrolyte 7 or may be disposed at an arbitrary position. Depending on the temperature of the solid electrolyte 7 detected by the temperature control means 23, the temperature control means 23 performs input control of the heater 22 constituting the heating means 21.

  The heat-insulating means 24 and 25 are heat-permeable heat insulating members for suppressing the loss of heat generated by the heater 22, and prevent heat diffusion of the heating means 21 and the oxygen pump element. Here, a heat insulating member molded into a flat plate mainly composed of silica and alumina was used. Each element constituting the oxygen supply device and the container 26 for maintaining the overall shape are provided with an opening 27 for ventilation on the negative electrode membrane side.

  A gas mixing means 29 is connected to the positive electrode film side of the container 26 through a vent 28. The mixing means 29 is composed of a gas induction pipe 30, a mixed gas introduction pipe 31, a gas mixer 32, and a gas pump 33. The mixing means 29 mixes oxygen generated through an oxygen pump element with air to give a predetermined oxygen. Use mixed gas of concentration.

  About the oxygen supply apparatus comprised as mentioned above, the operation | movement and an effect | action are demonstrated below.

  First, the oxygen supply device is placed in the atmosphere such as room air. At this time, atmospheric components such as nitrogen and oxygen (hereinafter simply referred to as nitrogen and oxygen) pass through the inside of the heat insulating means 24 and 25 which are air-permeable heat insulating materials, and on the positive electrode film 8 side and the negative electrode film 9. Stable in a diffused state to the surface on the side.

  When the heater 22 is energized by the temperature control means 23 in this state, the temperature of the solid electrolyte 7 in the heat insulation means 24 and 25 rises. The temperature control means 23 is energized while controlling the heater 22 so that the temperature required for the operation of the solid electrolyte 7 is about 600 ° C. However, this temperature is not limited, and an operation at an arbitrary temperature is possible according to the characteristics of the solid electrolyte 7.

  When a voltage is applied to each solid electrolyte 7 through the positive second electrode film 10 and the negative second electrode film 11 when the temperature at which the solid electrolyte 7 can conduct ions is reached, the vicinity of the surface on the negative electrode film 9 side The oxygen moves from the negative electrode film 9 to the positive electrode film 8 as oxygen ions from the negative electrode film 9 by an electrochemical reaction, and is released as oxygen molecules from the surface on the positive electrode film 8 side.

At this time, a current of 2.9 A flows through each solid electrolyte 7 by applying a voltage of about 0.7 V. Therefore, an oxygen pump element composed of 36 solid electrolytes 7 can be operated at 24 V to obtain about 370 ml / min of oxygen gas. At this time, the metal foil member 12 is also exposed to a high temperature state in addition to the atmospheric temperature of 600 ° C. The TiO ₂ film formed on the surface of the metal foil member 12 can effectively protect against the surface oxidation of the metal foil member 12. As the metal foil member 12, excellent oxidation resistance can be obtained by using ferritic stainless steel containing aluminum.

  The vicinity of the surface on the positive electrode film 8 side becomes a state close to pure oxygen by the generated oxygen gas, leaves the surface on the positive electrode film 8 side, passes through the heat insulating means 25 and is discharged. Therefore, the metal foil member 12 and the gas sealant 17 serving as a space partitioning unit effectively function as a unit for preventing gas leakage from the negative electrode film 9 side. In addition, the conductive film 13 for gas-sealing the solid electrolyte 7 and the metal foil member 12 also effectively acts as a means for preventing gas leakage from the negative electrode film 9 side.

  On the other hand, nitrogen is left on the negative electrode film 9 side. The remaining nitrogen diffuses into the atmosphere due to the air permeability of the heat insulating means 24, and oxygen is supplied from the outside together with new air to the negative electrode film 9 side.

  The oxygen gas released from the positive electrode film 8 side passes through the vent hole 28 and is mixed with the mixed gas by the gas induction pipe 30, the mixed gas introduction pipe 31, and the gas mixer 32 constituting the mixing means 29. Is done. In the present embodiment, the mixed gas is the atmosphere. The generated mixed gas is an oxygen-enriched gas, and its flow rate is determined by the suction and discharge speed of the gas pump 33.

  The oxygen concentration in the mixed gas is determined by the mixed gas flow rate and the amount of oxygen ions flowing through the solid electrolyte 7, that is, the magnitude of the ionic current. The ion current can be controlled by the magnitude of the voltage applied to the solid electrolyte 7.

  As described above, in the present embodiment, 36 solid electrolytes 7 are electrically connected in a series circuit, and the solid electrolyte is so formed that the positive electrode film 8 side and the negative electrode film 9 side develop oxygen ion conductivity. The metal foil member 12 suppresses gas leakage through the space 7 and performs heating heating and voltage application, thereby releasing oxygen molecules from the positive electrode film 8 side and generating an oxygen-enriched mixed gas. Thus, an arbitrary oxygen concentration gas can be stably obtained by voltage control by the voltage control means 20 and control of the mixed gas flow rate by the gas pump 33. When operating at 24 V, the oxygen concentration in the mixed gas obtained by the oxygen supply device in this embodiment can supply an oxygen concentration of 90%, 0.4 L / min to an oxygen concentration of 30%, and 3 L / min. there were.

(Embodiment 2)
4 and 5 show an oxygen pump element according to Embodiment 2 of the present invention. Since the basic configuration is the same as that of the first embodiment, differences will be described.

  In the present embodiment, the configurations of the first electrode film and the second electrode film formed on the surface of the solid electrolyte 34 are the same as those in the first embodiment. The dimensions of the solid electrolyte 34 are 31 × 31 mm and the thickness is 130 μm. Here, a positive electrode film (not shown), a positive second electrode film 36, a negative electrode film (not shown), and a negative second electrode film 37 are divided into four solid electrolytes 34 to form a capacitor. It is arranged in such a pair structure. The dimension of one positive second electrode film 36 and the negative second electrode film 37 among the four divided parts was 12 × 12 mm, and the distance between the adjacent electrode films was 2 mm. The metal foil member 35 is the same as that of the first embodiment, and nine openings and 28 × 28 mm are provided.

  The positive second electrode film 36 and the negative second electrode film 37 that are divided into four are configured to be electrically connected in series. As shown in the figure, the individual solid electrolytes 34 are numbered (1 to 36) in the order of potentials connected to a series circuit.

  Specifically, three through holes 38 are disposed at the center line position of one solid electrolyte 34, and the positive second electrode film 36 is located on the opposite side of the negative second electrode by using the through holes 38. The film 37 is electrically connected. The first negative second electrode film 37 is adjacent to the second positive second electrode film 36 and the second negative second electrode film 37 is connected to the third positive electrode film 37 using the through-hole 38 positioned at the center. The second electrode film 36 and the third negative second electrode film 37 are connected to the adjacent fourth positive second electrode film 36. The fourth negative second electrode film 36 is connected to a conductive film 39 where the solid electrolyte 34 is bonded to the metal foil member 35, and the conductive film 39 is provided with a portion protruding from the solid electrolyte 34. The fifth positive second electrode film 36 of the solid electrolyte 34 positioned and the gold wire 40 are connected. A voltage is applied to the lead portion 41 connected to be sequentially connected to the first positive second electrode film 36 and finally connected to the 36th negative second electrode film 37 so as to be electrically connected. By applying this, the oxygen pump element is operated.

  The solid electrolyte 34 is bonded to the metal foil member 35 by a conductive film 39 with a width of 1.5 mm. Screen printing so that the lead extraction part can be formed by using Au paste as the conductive film 39 in the opening part of the metal foil member 35 and printing 32 * 34 mm on the opening part 28 * 28 mm so as to protrude from the solid electrolyte 34. Was performed twice. Then, nine solid electrolytes 34 were joined to the metal foil member 35 by drying and firing at 750 ° C.

  The positive second electrode film 36 and the negative second electrode film 37 were connected simultaneously by screen printing of Au paste. Therefore, a manufacturing process for connecting the positive second electrode film 36 and the negative second electrode film 37 is not particularly added.

  And the oxygen supply apparatus similar to Embodiment 1 was produced using the oxygen pump element in this Embodiment. As a result, by operating at 26 V, a current of 2.9 A flowed and oxygen gas of about 370 ml / min could be obtained. Therefore, using the nine solid electrolytes 34, it was possible to obtain the same performance with the same current value as in the first embodiment. Since nine solid electrolytes 34 are arranged on the metal foil member 35 and a small number of gold wires 40 and lead portions 41 and 42 are connected, the manufacturing process is simplified as compared with the first embodiment. .

(Embodiment 3)
6 and 7 show an oxygen pump element according to Embodiment 3 of the present invention. Since the basic configuration is the same as that of the first embodiment, differences will be described.

  In the present embodiment, the configurations of the first electrode film and the second electrode film formed on the surface of the solid electrolyte 43 are the same as those in the first embodiment. The dimensions of the solid electrolyte 43 are 46 × 46 mm and the thickness is 200 μm. Here, a positive electrode film (not shown), a positive second electrode film 45, a negative electrode film (not shown), and a negative second electrode film 46 are divided into nine solid electrolytes 43 to form a capacitor. It is arranged in such a pair structure. The size of one positive second electrode film 45 and the negative second electrode film 46 out of the nine divisions was 12 × 12 mm, and the distance between adjacent electrode films was 2 mm. The metal foil member 44 is the same as that of the first embodiment, and four openings, 42 × 42 mm, are provided.

  The positive second electrode film 45 and the negative second electrode film 46 divided into nine are configured to be electrically connected in series. As shown in the figure, the individual solid electrolytes 43 are numbered (1 to 36) in the order of potentials connected to a series circuit.

  Specifically, eight through holes 47 are disposed in one solid electrolyte 43, and the positive second electrode film 45 is electrically connected to the negative second electrode film 46 located on the opposite side by using the through holes 47. Are connected sequentially. The ninth negative second electrode film 46 is connected to a conductive film 48 to which the solid electrolyte 43 is bonded to the metal foil member 44, and the conductive film 48 is provided with a portion protruding from the solid electrolyte 43, and adjacent to the conductive film 48. The tenth positive second electrode film 45 of the solid electrolyte 43 positioned is connected to the gold wire 49. Further, the voltage is applied to the lead portion 51 that is connected in order in the same manner and is finally connected to the lead portion 50 connected to the first positive second electrode film 45 and the 36th negative second electrode film 46. Is applied to operate the oxygen pump element.

  The solid electrolyte 43 is bonded to the metal foil member 44 by a conductive film 48 with a width of 2 mm. Using Au paste as the conductive film 48 at the opening of the metal foil member 44, printing is performed at 47 × 49 mm for the opening 42 × 42 mm, so that it protrudes from the solid electrolyte 43 and screen printing is performed so that a lead extraction portion can be formed. Was performed twice. Then, the four solid electrolytes 43 were joined to the metal foil member 44 by drying and firing at 750 ° C.

  The positive second electrode film 45 and the negative second electrode film 46 were simultaneously connected by screen printing of Au paste. Therefore, a manufacturing process for connecting the positive second electrode film 45 and the negative second electrode film 46 is not particularly added.

  And the oxygen supply apparatus similar to Embodiment 1 was produced using the oxygen pump element in this Embodiment. As a result, by operating at 32 V, a current of 2.9 A flowed, and oxygen gas of about 370 ml / min could be obtained. Therefore, using the four solid electrolytes 43, it was possible to obtain the same performance with the same current value as in the first embodiment. Since the four solid electrolytes 43 are arranged on the metal foil member 44 and a smaller number of the gold wires 49 and the lead portions 50 and 51 are connected, the manufacturing process is further simplified as compared with the first embodiment. ing.

  In each of the first to third embodiments described above, lanthanum gallate is used as the solid electrolytes 7, 34, and 43. However, the present invention is not limited to this. It may be. However, at present, the lanthanum gallate material is the most preferable material in view of the durability of the material because the operating temperature is low as an oxygen ion conductor.

Further, although Sm _0.5 Sr _0.5 CoO ₃ is used as the composite metal oxide of the first electrode film (positive electrode film 8 and negative electrode film 9), it is not limited to this. However, since the composite metal oxide having a perovskite structure has high electrode reactivity with oxygen molecules and itself has conductivity, excellent oxygen ion conductivity can be realized. In particular, among the perovskite complex oxides, those composed of at least one of lanthanum and samarium at the A site and at least one of cobalt, iron, and manganese at the B site, and a part of the A site replaced with strontium It had excellent conductivity and high oxygen molecule electrode reactivity.

  Moreover, although the material of Fe-20Cr-5Al was used as the metal foil members 12, 35, and 44, it is not limited to this, and other metal foil materials are used as long as the material has durability against high-temperature oxidation. can do. However, at present, ferritic stainless steel containing aluminum has excellent characteristics against high-temperature oxidation. Furthermore, it is possible to add a rare earth metal for the purpose of improving high temperature oxidation resistance. Moreover, although 12 micrometers in thickness was used, it is thought that 5-20 micrometers is preferable as a metal foil member. That is, in order to prevent the heat generated in the solid electrolyte from being transferred to the outer peripheral portion, the thinner the thickness, the better. However, if the thickness is 5 μm or less, the handling at the time of manufacture becomes worse.

The metal foil member 12,35,44 which is coated with an insulating film, was used which was formed of TiO ₂ film in a liquid phase deposition method is not limited thereto. In addition, a ZrO ₂ film or an Al ₂ O ₃ film can be used. These were able to form a thin oxide film in a short time by being immersed in the treatment aqueous solution, and were able to maintain sufficient insulation even in a high temperature atmosphere in which the oxygen pump element was operated. Since the insulating film is a very thin film, the solid electrolyte can be prevented from peeling from the metal foil member without impairing the flexibility of the metal foil member, and the insulation necessary for making the solid electrolyte into a series circuit can be maintained. I was able to.

  Moreover, although it demonstrated only about the case where it was joined to the negative electrode film | membrane 9 side as a structure of the metal foil members 12, 35, and 44, and it used as a partition means to partition a space part, conversely on the positive electrode film | membrane 8 side. It may be used as a partitioning means for joining and partitioning the space.

  In addition, Au-based materials are used for the positive second electrode films 10, 36, 45 and the conductive films 13, 39, 48. However, the present invention is not limited to this, and any other material having a low resistance and heat resistance can be used. Ag-based and AgPd-based materials can be used.

  Moreover, although the case where the second electrode film is further arranged on the positive electrode film and the negative electrode film on the surface of the solid electrolyte has been described, the present invention can be applied to a structure in which the second electrode film is not arranged. For example, if the size of the electrode film formed on the surface of the solid electrolyte is 5 × 5 mm, the current value to be passed is about 0.5 A, and the potential unevenness generated on the electrode film is not so large, so the second electrode film is necessary. Don't be.

  As described above, the oxygen pump element according to the present invention and the oxygen supply device using the oxygen pump element can accumulate the voltage applied to the solid electrolyte, and can be operated with a general-purpose power source with a high voltage and a small current. Therefore, it can be applied to a wide range of uses such as an air purifier, an air conditioner, a health promoting device, and a health promoting device using oxygen.

Sectional drawing which shows the solid electrolyte of the oxygen pump element in Embodiment 1 of this invention Top view of the oxygen pump element Sectional view of an oxygen supply device using the oxygen pump element The top view of the positive electrode side of the oxygen pump element in Embodiment 2 of this invention Plan view on the negative electrode side of the oxygen pump element The top view of the positive electrode side of the oxygen pump element in Embodiment 3 of this invention Plan view on the negative electrode side of the oxygen pump element Plan view of an oxygen pump element showing a conventional example Sectional view of an oxygen supply device using the oxygen pump element

Explanation of symbols

7, 34, 43 Solid electrolyte 8 Positive electrode film 9 Negative electrode film 10, 36, 45 Positive second electrode film 11, 37, 46 Negative second electrode film 12, 35, 44 Metal foil member 13, 39, 48 Conductive film 14, 40, 49 Gold wire 15, 16, 41, 42, 50, 51 Lead part 19 Voltage application means 20 Voltage control means 21 Heating means 23 Temperature control means 24, 25 Heat insulation means 29 Mixing means 38, 47 Through hole

Claims (13)

The metal foil member covered with an insulating film has a plurality of openings, and a plurality of oxygen ion conductive solid electrolytes are gas-sealed in the openings, and a positive electrode film and a negative electrode are disposed on both sides of the solid electrolyte. An oxygen pump element in which a membrane is formed, and the plurality of solid electrolytes are configured such that the positive electrode film and the negative electrode film are electrically connected in series. In one solid electrolyte, a positive electrode film and a negative electrode film are arranged in a pair structure in which a capacitor is formed by dividing the positive electrode film and the negative electrode film so that the positive electrode film and the negative electrode film are electrically connected in series. The oxygen pump element according to claim 1, which is configured as follows. 2. The gas seal is formed such that the periphery of the opening of the metal foil member and the outer periphery of the solid electrolyte are joined by a conductive film, and at least one positive electrode film or negative electrode film is electrically connected to the conductive film. Or the oxygen pump element of 2. A lead part is connected to the conductive film which is a gas seal between the metal foil member and the solid electrolyte, and at least one positive electrode film or negative electrode film on the solid electrolyte, and the lead part is flush with the metal foil member surface. The oxygen pump element according to any one of claims 1 to 3, which is taken out from a direction. The positive electrode film and the negative electrode film formed on both surfaces of one solid electrolyte are connected through a through-hole provided in the solid electrolyte to form a series circuit. The oxygen pump element described in 1. The oxygen pump element according to any one of claims 1 to 5, wherein the single metal foil member is configured as partition means for partitioning a space in which the solid electrolyte is located. The positive electrode film and the negative electrode film are composed of a first electrode film directly bonded to the solid electrolyte and a second electrode film formed on the first electrode film, and the first electrode film is a composite on the solid electrolyte. The oxygen pump element according to any one of claims 1 to 6, wherein the second electrode film is a film mainly containing a noble metal component. The oxygen pump element according to any one of claims 1 to 7, wherein the solid electrolyte is lanthanum gallate. The oxygen pump element according to claim 7 or 8, wherein the composite metal oxide of the first electrode film has a perovskite structure. The oxygen pump element according to any one of claims 3 to 9, wherein the conductive film is composed mainly of a noble metal component. The oxygen pump element according to any one of claims 1 to 10, wherein the metal foil member is ferritic stainless steel containing aluminum. Oxygen pump element according to any one of claims 1-11 insulating film is TiO ₂ film or ZrO ₂ film formed by a liquid phase precipitation method the metal foil member surface. The oxygen pump element according to any one of claims 1 to 11, a voltage applying means for applying a voltage to the oxygen pump element, a voltage control means for controlling the voltage applying means, and heating the oxygen pump element. Heating means, temperature control means for detecting the temperature of the oxygen pump element and controlling the heating means, heat insulating means for preventing thermal diffusion of the heating means and the oxygen pump element, and the oxygen pump element An oxygen supply device comprising mixing means for mixing oxygen generated in this way with air to make a mixed gas having a predetermined oxygen concentration.