WO2020195681A1 - 酸素センサ及びそれを具備する微小機械電気素子 - Google Patents

酸素センサ及びそれを具備する微小機械電気素子 Download PDF

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WO2020195681A1
WO2020195681A1 PCT/JP2020/009431 JP2020009431W WO2020195681A1 WO 2020195681 A1 WO2020195681 A1 WO 2020195681A1 JP 2020009431 W JP2020009431 W JP 2020009431W WO 2020195681 A1 WO2020195681 A1 WO 2020195681A1
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electrode
solid electrolyte
oxygen
electrolyte membrane
membrane
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PCT/JP2020/009431
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English (en)
French (fr)
Japanese (ja)
Inventor
広平 加藤
慎吾 井手
旬春 大山
康博 瀬戸
八島　勇
憲剛 島ノ江
賢 渡邉
昂一 末松
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三井金属鉱業株式会社
国立大学法人九州大学
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Priority to JP2021508925A priority Critical patent/JP7588580B2/ja
Publication of WO2020195681A1 publication Critical patent/WO2020195681A1/ja
Priority to JP2024063710A priority patent/JP2024074981A/ja

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/409—Oxygen concentration cells

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  • the present invention relates to an oxygen sensor and a micromechanical electric element including the oxygen sensor.
  • Patent Document 1 describes an electromotive force oxygen sensor composed of an electrochemical oxygen pump unit, a sealed space, and an electrochemical sensor unit.
  • an external voltage is applied between both electrodes of the electrochemical oxygen pump section, and the oxygen gas existing in the sealed space is forcibly discharged to the outside according to the principle of the electrochemical oxygen pump, and the reference gas chamber is defined. It is controlled to the low oxygen partial pressure of.
  • Patent Document 2 describes an oxygen sensor in which an electric current is applied between an outer electrode and an inner electrode to introduce oxygen in a detection gas in the vicinity of the inner electrode, and the introduced oxygen is used as a reference gas. Has been done.
  • a relaxation layer having a porous structure containing zirconia and aluminum is provided on the outer surface of the inner electrode, and oxygen is introduced into the relaxation layer. It is possible to enter.
  • the oxygen sensor of Patent Document 1 attempts to accurately measure the oxygen concentration in the test gas by controlling the oxygen partial pressure in the reference gas chamber to a low standard.
  • the oxygen partial pressure in the reference gas chamber is controlled to a low value, even a slight change in the oxygen partial pressure greatly affects the electromotive force, so it is not easy to improve the detection accuracy. ..
  • the oxygen sensor described in Patent Document 2 uses the oxygen as a reference gas by making the partial pressure of oxygen introduced in the vicinity of the inner electrode higher than the partial pressure of oxygen in the atmosphere, and uses a columnar element. Is forming. Due to this, it is necessary to make the relaxation layer porous and high strength. However, making the relaxation layer porous and having high strength is disadvantageous in terms of miniaturization of the oxygen sensor. It is not easy to apply the formation of such a porous layer or the production of a columnar element to, for example, a micromechanical electric element called MEMS (MicroElectro Mechanical Systems).
  • MEMS MicroElectro Mechanical Systems
  • An object of the present invention is to provide an oxygen sensor capable of eliminating various drawbacks of the above-mentioned prior art.
  • the present invention comprises a first solid electrolyte membrane having oxide ion conductivity and a first membrane electrode assembly provided with a first electrode arranged on one surface of the solid electrolyte membrane.
  • a second solid electrolyte membrane having oxide ion conductivity and a second membrane electrode assembly having a second electrode arranged on one surface of the solid electrolyte membrane are provided. The first membrane electrode assembly and the second membrane electrode assembly so that the first solid electrolyte membrane in the first membrane electrode assembly and the second solid electrolyte membrane in the second membrane electrode assembly face each other at intervals.
  • An intermediate electrode is arranged between the first solid electrolyte membrane in the first membrane electrode assembly and the second solid electrolyte membrane in the second membrane electrode assembly so as to be in contact with both solid electrolyte films.
  • the reference oxygen concentration space is defined by the wall part that allows oxygen to pass through so as to surround the intermediate electrode.
  • the first electrode is arranged so that the first electrode faces the atmosphere to be measured, and the intermediate electrode is connected to the positive electrode of the power supply and the second electrode is connected to the negative electrode of the power supply to provide oxygen in the reference oxygen concentration space. It is configured to measure the oxygen concentration in the atmosphere to be measured facing the first electrode by measuring the electromotive force generated between the first electrode and the intermediate electrode while keeping the concentration increased. It provides an oxygen sensor.
  • the present invention includes a membrane electrode assembly having a solid electrolyte membrane having oxide ion conductivity and a first electrode and a second electrode arranged on each surface of the solid electrolyte membrane.
  • the electrode facing member is arranged so as to face the second electrode.
  • a reference oxygen concentration space is defined by a wall portion provided between the solid electrolyte membrane and the member so as to surround the second electrode. At least one of the member and the wall portion is made of a material capable of permeating oxygen.
  • the first electrode is arranged so that the first electrode faces the atmosphere to be measured, the second electrode is connected to the positive electrode of the power supply, and the first electrode is connected to the negative electrode of the power supply to form oxygen in the reference oxygen concentration space.
  • the first electrode is placed in a high concentration state, the connection of the first electrode and the second electrode to the power supply is disconnected, and the electromotive force generated between the first electrode and the second electrode is measured. It provides an oxygen sensor for measuring the oxygen concentration in the atmosphere to be measured facing the electrode.
  • the present invention includes a solid electrolyte membrane having oxide ion conductivity, a first electrode and a second electrode arranged on one surface of the solid electrolyte membrane, and an intermediate electrode arranged on the other surface of the solid electrolyte membrane.
  • An electrode facing member is arranged so as to face the intermediate electrode.
  • a reference oxygen concentration space is defined by a wall portion provided between the solid electrolyte membrane and the member so as to surround the intermediate electrode. At least one of the member and the wall portion is made of a material capable of permeating oxygen.
  • the first electrode and the second electrode are arranged so that the first electrode faces the measurement target atmosphere and the second electrode faces the measurement target atmosphere or the outside air, and the intermediate electrode is connected to the positive electrode of the power supply.
  • the second electrode is connected to the negative electrode of the power supply, the oxygen concentration in the reference oxygen concentration space is increased, and the electromotive force generated between the first electrode and the intermediate electrode is measured. Therefore, an oxygen sensor for measuring the oxygen concentration in the atmosphere to be measured facing the first electrode is provided.
  • FIG. 1 is a schematic view showing the structure of an embodiment of the oxygen sensor of the present invention.
  • FIG. 2 is a graph showing how the relationship between the concentration of oxygen gas in the test gas and the electromotive force of the concentration cell depends on the concentration of oxygen gas contained in the reference gas.
  • FIG. 3 is a schematic diagram showing the structure of another embodiment of the oxygen sensor of the present invention.
  • FIG. 4 is a schematic view showing the structure of still another embodiment of the oxygen sensor of the present invention.
  • FIG. 5 is a schematic view showing the structure of still another embodiment of the oxygen sensor of the present invention.
  • FIG. 6 is a graph showing a change over time in voltage when measuring the concentration of oxygen gas using the oxygen sensor of the embodiment shown in FIG.
  • FIG. 7 is a schematic view showing the structure of still another embodiment of the oxygen sensor of the present invention.
  • FIG. 8 is a schematic view showing the structure of still another embodiment of the oxygen sensor of the present invention.
  • FIG. 1 shows an embodiment of the oxygen sensor of the present invention.
  • the oxygen sensor 1 shown in the figure includes a first membrane electrode assembly 10 and a second membrane electrode assembly 20.
  • the first membrane electrode assembly 10 includes a first solid electrolyte membrane 100 having oxide ion conductivity and a first electrode 101 arranged on one surface of the solid electrolyte membrane 100.
  • the second membrane electrode assembly 20 includes a second solid electrolyte membrane 200 having oxide ion conductivity and a second electrode 102 arranged on one surface of the solid electrolyte membrane 200.
  • the first solid electrolyte membrane 100 and the second solid electrolyte membrane 200 may be made of the same type or different materials as long as they have the conductivity of oxide ions.
  • the first electrode 101 and the second electrode 102 may be made of the same type of material or different materials as long as they have conductivity.
  • FIG. 1 shows a state in which the first solid electrolyte membrane 100 and the second solid electrolyte membrane 200, which are both flat plates, are arranged substantially in parallel with a certain distance between them.
  • the distance between the first solid electrolyte membrane 100 and the second solid electrolyte membrane 200 is not critical in the present invention, and may be set to an appropriate value according to the size of the oxygen sensor 1, the usage situation, and the like. Generally, if the distance between the first solid electrolyte membrane 100 and the second solid electrolyte membrane 200 is set to 0.05 mm or more and 10 mm or less, the oxygen gas concentration can be measured with high accuracy.
  • both solid electrolyte membranes 100 and 200 are formed.
  • the intermediate electrode 120 is arranged so as to be in contact with both.
  • the intermediate electrode 120 may be made of the same material as the first electrode 101 and the second electrode 102 described above, or may be made of a different material as long as it has conductivity.
  • the annular wall portion 30 through which oxygen can permeate between the first solid electrolyte membrane 100 in the first membrane electrode assembly 10 and the second solid electrolyte membrane 200 in the second membrane electrode assembly 20.
  • the annular wall portion 30 has a structure capable of allowing oxygen gas to flow inside and outside the wall portion.
  • the annular wall portion 30 is provided so as to surround the intermediate electrode 120.
  • a reference oxygen concentration space S is defined between the first solid electrolyte membrane 100 and the second solid electrolyte membrane 200 by the annular wall portion 30.
  • the reference oxygen concentration space S is defined by the annular wall portion 30, the first solid electrolyte membrane 100, the second solid electrolyte membrane 200, and the intermediate electrode 120.
  • the reference oxygen concentration space S communicates with the outside world through an annular wall portion 30 made of a material that allows oxygen to permeate, for example, a porous material.
  • the volume of the reference oxygen concentration space S is not critical in the present invention, and may be set to an appropriate value according to the size of the oxygen sensor 1, the usage situation, and the like. Generally, if the volume of the reference oxygen concentration space S is set to 0.01 mm 3 or more and 1000 mm 3 or less, the oxygen gas concentration can be measured with high accuracy.
  • the intermediate electrode 120 is made of a porous material or the like and has voids, the voids can be used as the reference oxygen concentration space S. Therefore, it is not necessary to provide a complete space between the intermediate electrode 120 and the annular wall portion 30.
  • the shape of the cross section of the annular wall portion 30 is not particularly limited as long as it is annular.
  • a tubular annular wall portion having a circular or rectangular cross section can be used.
  • the shape of the annular wall portion 30 to be used may be appropriately selected according to the shapes of the solid electrolyte membranes 100 and 200, the size of the oxygen sensor 1, and the like.
  • the first solid electrolyte membrane 100 and the first electrode 101 and the intermediate electrode 120 arranged on each surface thereof constitute the first single cell.
  • the second solid electrolyte membrane 200 and the second electrode 102 and the intermediate electrode 120 arranged on each surface thereof constitute the second single cell.
  • the intermediate electrode 120 also serves as an electrode of the first single cell and an electrode of the second single cell.
  • the first single cell acts as a concentration cell.
  • the second single cell acts as an oxygen pump.
  • a voltmeter 60 is connected between the first electrode 101 and the intermediate electrode 120 in the first single cell, and the electromotive force generated between both electrodes of the concentration cell can be measured. There is.
  • a DC power supply 40 is connected between the second electrode 102 and the intermediate electrode 120, and a voltage is applied between both electrodes.
  • the intermediate electrode 120 is connected to the positive electrode of the DC power supply 40
  • the second electrode 102 is connected to the negative electrode of the DC power supply 40.
  • the method of measuring the oxygen concentration in the test gas by the oxygen sensor 1 having the above configuration is as described below.
  • these electrodes are arranged so that the first electrode 101 faces the atmosphere to be measured and the second electrode 102 faces the outside air (generally the atmosphere).
  • the entire oxygen sensor 1 is heated so that oxide ion conductivity is exhibited in the first and second solid electrolyte membranes 100 and 200.
  • the heating temperature differs depending on the constituent materials of the first and second solid electrolyte membranes 100 and 200. For example, when the first and second solid electrolyte membranes 100 and 200 are constructed from the materials described later, the temperature may be less than about 600 ° C. Practical oxide ion conductivity is exhibited.
  • the heating temperature is preferably 200 ° C.
  • Sufficient measurement accuracy can be obtained by heating the entire oxygen sensor 1 to bring the first and second solid electrolyte membranes 100 and 200 to the above temperatures or higher. It should be noted that this temperature is not the set temperature, but the actual temperature of the first and second solid electrolyte membranes 100 and 200.
  • the intermediate electrode 120 is connected to the positive electrode of the DC power supply 40 and the second electrode 102 is connected to the negative electrode of the DC power supply 40.
  • the oxygen pumping action of the second single cell is exhibited, and the oxygen gas contained in the outside air is reduced to oxide ions.
  • the oxide ions move in the second solid electrolyte membrane 200 and reach the intermediate electrode 120.
  • the oxide ion that reaches the intermediate electrode 120 emits an electron and changes into an oxygen gas.
  • the oxygen gas generated in this way is accumulated in the reference oxygen concentration space S.
  • the reference oxygen concentration space S since a part of the reference oxygen concentration space S is defined by an annular wall portion 30 made of a material that allows oxygen to permeate, and the reference oxygen concentration space S communicates with the outside, the reference oxygen concentration space S.
  • the pressure in S does not rise excessively.
  • the partial pressure of the oxygen gas becomes high while maintaining a certain pressure.
  • the oxygen concentration in this state is called the reference oxygen concentration.
  • the reference oxygen concentration is 100 vol% of oxygen from the viewpoint of high-precision measurement. Whether or not the oxygen concentration in the space S is 100 vol% is determined by measuring the electromotive force between the electrodes under a known test gas concentration atmosphere such as an oxygen concentration of 20.9% in a normal atmosphere. Can be judged by.
  • the electromotive force generated between the first electrode 101 and the intermediate electrode 120 in the first single cell is measured by the voltmeter 60.
  • a DC voltage is continuously applied between the second electrode 102 and the intermediate electrode 120 in the second single cell to maintain the oxygen concentration in the reference oxygen concentration space S at a certain high state. ..
  • the concentration of oxygen gas in the atmosphere to be measured is calculated from the Nernst equation shown below.
  • E (RT / 4F) ln ( PO2 A / PO2 B )
  • E the electromotive force (V) generated between the first electrode 101 and the intermediate electrode 120
  • R represents the gas constant
  • T represents the absolute temperature (K)
  • F represents the Faraday constant
  • PO2 A represents the concentration of oxygen gas in the atmosphere to be measured
  • PO2 B represents the concentration of oxygen gas in the reference oxygen concentration space S. Since E, R, T, F and PO2 B are known in the above formula, PO2 A , that is, the concentration of oxygen gas in the atmosphere to be measured can be calculated.
  • FIG. 1 is a graph depicting the relationship between the oxygen gas concentration and the electromotive force of the oxygen sensor 1 of the present embodiment according to the Nernst equation.
  • the electromotive force differs by more than 10 mV, and it is calculated due to this.
  • the concentration of oxygen gas produced also differs greatly.
  • the straight lines C to E it is understood that there is almost no difference in the electromotive force even when the reference oxygen concentration differs by up to 20 vol%. Due to this, the calculated oxygen gas concentrations are also almost the same.
  • the measurement accuracy can be improved by measuring the oxygen gas concentration in a state where the reference oxygen concentration is high.
  • the absolute value of the electromotive force is higher in the region where the concentration of oxygen gas in the test gas is lower, which is the concentration region where measurement errors are likely to occur. Since it becomes large, there is an advantage that an error is unlikely to occur in the measurement even if the oxygen gas concentration is low.
  • the oxygen sensor 1 of the present embodiment does not use the atmosphere as a reference gas for the concentration cell, unlike the conventional one, it is less susceptible to the influence of impurities contained in the atmosphere. This also makes it possible to measure the concentration of oxygen gas with high accuracy.
  • the concentration of oxygen gas in the reference oxygen concentration space S is preferably 60 vol% or more and 100 vol% or less, more preferably 80 vol% or more and 100 vol% or less, still more preferably 90 vol% or more and 100 vol. It is advantageous to measure the oxygen gas concentration under the condition set to% or less.
  • the oxygen gas concentration in the reference oxygen concentration space S is measured by measuring the electromotive force between the electrodes under a known test gas concentration atmosphere such as, for example, an oxygen concentration of 20.9% in the normal atmosphere.
  • the voltage of the DC power supply is preferably set to 0.05 V or more and 3 V or less, or the volume of the reference oxygen concentration space S is 0.01 mm. It may be set to 3 or more and 800 mm 3 or less, or the amount of oxygen permeating through the annular wall portion 30 may be reduced.
  • the pressure (Pa) in the reference oxygen concentration space S is compared with the air pressure (Pa) in the atmosphere to be measured (that is, the pressure (Pa) in the reference oxygen concentration space S / the air pressure in the atmosphere to be measured (that is).
  • the value of Pa)) is preferably 1.0 or more and 3.0 or less, more preferably 1.0 or more and 2.0 or less, and even more preferably 1.0 or more and 1.5 or less. It is advantageous to measure the concentration.
  • the voltage of the DC power supply is preferably set to 1.0 V or more and 3.0 V or less, or the volume of the reference oxygen concentration space S is 0.01 mm 3. It may be set to 1000 mm 3 or less, or the amount of oxygen permeating through the annular wall portion 30 may be adjusted.
  • the method of adjusting the oxygen gas concentration and the pressure in the reference oxygen concentration space S can be applied to another embodiment of the oxygen sensor described later.
  • FIG. 3 shows another embodiment of the oxygen sensor shown in FIG.
  • the intermediate electrode 120 provided in the oxygen sensor shown in FIG. 1 is in contact only with the third electrode 103 in which the first solid electrolyte membrane 100 is in contact with the second solid electrolyte membrane 200. It is different from the oxygen sensor 1 shown in FIG. 1 in that it is divided into the fourth electrodes 104 and are independent of each other. By making the electrodes independent, deterioration of the electrodes is less likely to occur, so that the life of the sensor can be expected to be improved.
  • the first membrane electrode assembly 10 in the oxygen sensor 1 shown in FIG. 3 includes a first solid electrolyte membrane 100, and first electrodes 101 and third electrodes 103 arranged on each surface of the solid electrolyte membrane 100.
  • the second membrane electrode assembly 20 includes a second solid electrolyte membrane 200, and a second electrode 102 and a fourth electrode 104 arranged on each surface of the solid electrolyte membrane 200.
  • the first electrode 101 to the fourth electrode 104 may be made of the same type of material or different materials as long as they have conductivity.
  • the first membrane electrode assembly 10 is such that the third electrode 103 in the first membrane electrode assembly 10 and the fourth electrode 104 in the second membrane electrode assembly 20 face each other with a gap. And the second membrane electrode assembly 20 are arranged.
  • FIG. 1 shows a state in which the third electrode 103 and the fourth electrode 104, which are both flat plates, are arranged substantially in parallel with a certain distance between them.
  • the distance between the third electrode 103 and the fourth electrode 104 is not critical in the present invention, and may be set to an appropriate value according to the size of the oxygen sensor 1, the usage situation, and the like. Generally, if the distance between the third electrode 103 and the fourth electrode 104 is set to 0.05 mm or more and 10 mm or less, the oxygen gas concentration can be measured with high accuracy.
  • the annular wall portion 30 is provided so as to surround the third electrode 103 and the fourth electrode 104.
  • a reference oxygen concentration space S is defined between the first solid electrolyte membrane 100 and the second solid electrolyte membrane 200 by the annular wall portion 30.
  • the reference oxygen concentration space S is defined by the annular wall portion 30, the first solid electrolyte membrane 100, the second solid electrolyte membrane 200, the third electrode 103, and the fourth electrode 104. ..
  • the reference oxygen concentration space S communicates with the outside world through an annular wall portion 30 made of a material through which oxygen gas can permeate.
  • the first membrane electrode assembly 10 constitutes a single cell.
  • the second membrane electrode assembly 20 also constitutes a single cell.
  • the first membrane electrode assembly 10 acts as a concentration cell.
  • the second membrane electrode assembly 20 acts as an oxygen pump.
  • a voltmeter 60 is connected between the first electrode 101 and the third electrode 103 in the first membrane electrode assembly 10, and the electromotive force generated between both electrodes of the concentration cell can be measured. It has become like.
  • a DC power supply 40 is connected between the second electrode 102 and the fourth electrode 104, and a voltage is applied between both electrodes.
  • the fourth electrode 104 is connected to the positive electrode of the DC power supply 40
  • the second electrode 102 is connected to the negative electrode of the DC power supply 40.
  • the method of measuring the oxygen concentration in the test gas by the oxygen sensor 1 shown in FIG. 3 is as described below.
  • these electrodes are arranged so that the first electrode 101 faces the atmosphere to be measured and the second electrode 102 faces the outside air (generally the atmosphere). Under this state, the entire oxygen sensor 1 is heated so that oxide ion conductivity is exhibited in the first and second solid electrolyte membranes 100 and 200.
  • the fourth electrode 104 is connected to the positive electrode of the DC power supply 40, and the second electrode 102 is connected to the negative electrode of the DC power supply 40.
  • the oxygen pumping action of the second membrane electrode assembly 20 is exhibited, and the oxygen gas contained in the outside air is reduced to become oxide ions.
  • the oxide ion moves in the second solid electrolyte membrane 200, reaches the fourth electrode 104, and changes to oxygen gas.
  • the oxygen gas generated in this way is accumulated in the reference oxygen concentration space S.
  • the partial pressure of the oxygen gas becomes high while maintaining a certain pressure.
  • the electromotive force generated between the first electrode 101 and the third electrode 103 in the first membrane electrode assembly 10 is measured by a voltmeter 60 and measured according to the above-mentioned Nernst equation. Calculate the concentration of oxygen gas in the target atmosphere.
  • FIG. 4 shows yet another embodiment of the oxygen sensor shown in FIG. Similar to the oxygen sensor shown in FIG. 1, the oxygen sensor 1 shown in FIG. 4 includes a first membrane electrode assembly 10 and a second membrane electrode assembly 20.
  • the first membrane electrode assembly 10 includes a first solid electrolyte membrane 100 and a first electrode 101 arranged on one surface of the solid electrolyte membrane 100.
  • the second membrane electrode assembly 20 includes a second solid electrolyte membrane 200 and a second electrode 102 arranged on one surface of the solid electrolyte membrane 200.
  • the arrangement of the first membrane electrode assembly 10 and the second membrane electrode assembly 20 is different from that of the embodiment shown in FIG. Specifically, of the two surfaces of the first solid electrolyte membrane 100, the surface on which the first electrode 101 is arranged and the surface of the two surfaces of the second solid electrolyte membrane 200 on which the second electrode 102 is arranged.
  • the first membrane electrode assembly 10 and the second membrane electrode assembly 20 are arranged so that they face each other with a gap.
  • the intermediate electrode 120 is arranged so as to be in contact with both the surface of the first solid electrolyte membrane 100 on which the first electrode 101 is arranged and the surface of the second solid electrolyte membrane 200 on which the second electrode 102 is arranged. There is.
  • the first electrode 101 is not in contact with the second solid electrolyte membrane 200, and the second electrode 102 is not in contact with the first solid electrolyte membrane 100. Therefore, with respect to the first solid electrolyte membrane 100, the first electrode 101 and the intermediate electrode 120 are arranged on the same surface of the first solid electrolyte membrane 100, and with respect to the second solid electrolyte membrane 200, the second solid electrolyte.
  • the second electrode 102 and the intermediate electrode 120 are arranged on the same surface of the film 200.
  • the first electrode 101 and the second electrode 102 are not arranged so as to overlap each other when viewed along the thickness direction of the oxygen sensor 1, that is, the vertical direction of the paper surface in the figure. Instead of, both electrodes 101 and 102 may be arranged so as to overlap each other.
  • the first solid electrolyte membrane 100, the first electrode 101, and the intermediate electrode 120 constitute the first single cell.
  • the second solid electrolyte membrane 200, the second electrode 102, and the intermediate electrode 120 constitute the second single cell.
  • the first single cell acts as a concentration cell.
  • the second single cell acts as an oxygen pump.
  • a voltmeter 60 is connected between the first electrode 101 and the intermediate electrode 120 in the first single cell, and the electromotive force generated between both electrodes of the concentration cell can be measured.
  • a DC power supply 40 is connected between the second electrode 102 and the intermediate electrode 120, and a voltage is applied between both electrodes.
  • the intermediate electrode 120 is connected to the positive electrode of the DC power supply 40
  • the second electrode 102 is connected to the negative electrode of the DC power supply 40.
  • the method of measuring the oxygen concentration in the test gas by the oxygen sensor 1 shown in FIG. 4 is as described below.
  • these electrodes are arranged so that the first electrode 101 faces the measurement target atmosphere and the second electrode 102 faces the measurement target atmosphere or the outside air (generally the atmosphere).
  • the entire oxygen sensor 1 is heated so that oxide ion conductivity is exhibited in the first and second solid electrolyte membranes 100 and 200.
  • the intermediate electrode 120 is connected to the positive electrode of the DC power supply 40, and the second electrode 102 is connected to the negative electrode of the DC power supply 40.
  • the oxygen pumping action of the second single cell is exhibited, and the oxygen gas is accumulated in the reference oxygen concentration space S.
  • the electromotive force generated between the first electrode 101 and the intermediate electrode 120 is measured by a voltmeter 60, and the concentration of oxygen gas in the atmosphere to be measured is measured according to the above-mentioned Nernst equation. calculate.
  • the oxygen sensor 1 of the present embodiment also measures the concentration of oxygen gas in the atmosphere to be measured with the reference oxygen concentration increased, it has an advantageous effect that the measurement accuracy can be improved.
  • the first electrode 101 and the intermediate electrode 120 are arranged on the same surface of the first solid electrolyte film 100, and the second electrode 101 and the intermediate electrode 120 are arranged on the same surface of the second solid electrolyte film 200. Since the electrode 102 and the intermediate electrode 120 are arranged, there is an advantage that the manufacturing process of the oxygen sensor 1 can be simplified.
  • the first solid electrolyte membrane 100 and the second solid electrolyte membrane 200 a material having oxide ion conductivity can be used without particular limitation.
  • at least one of the first solid electrolyte membrane 100 and the second solid electrolyte membrane 200 is A, M and O (A is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, One or more elements selected from the group consisting of Er, Yb, Lu, Be, Mg, Ca, Sr and Ba.
  • M is Mg, Al, Sc, Ti, V, Cr, Mn, Fe.
  • the first solid electrolyte membrane 100 is made of a compound containing A, M and O, it is preferable because the transport number of oxide ions can be increased and a stable electromotive force can be obtained.
  • At least one of the first solid electrolyte membrane 100 and the second solid electrolyte membrane 200 has a general formula: A 9.33 + x [T 6.00- y My ] O 26.0 + z (A in the formula is La, Ce. , Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Be, Mg, Ca, Sr and Ba.
  • T in the formula is an element containing Si, Ge, or both.
  • M in the formula is Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Ga, Y, Zr.
  • the compound contains a composite oxide having a molar ratio of 1.33 or more and 3.61 or less.
  • the second solid electrolyte membrane 200 used for the second membrane electrode assembly 20 that acts as an oxygen pump is represented by the general formula: A 9.33 + x [T 6.00- y My ] O 26.0 + z. When it is composed of a compound containing a composite oxide, the oxygen pumping action is remarkably exhibited at a lower temperature, which is preferable.
  • a 9.33 + x [T 6.00 -y M y] O 26.0 + compound represented by z is oriented apatite type oxide ion conductor, degree of orientation measured by the Lotgering method is It is preferably 0.6 or more from the viewpoint of increasing the oxide ion conductivity.
  • the thicknesses of the first solid electrolyte membrane 100 and the second solid electrolyte membrane 200 are not critical in the present invention, and may have enough strength to withstand the use of the oxygen sensor 1.
  • the thickness of these electrolyte membranes can generally be 0.1 ⁇ m or more and 1.0 mm or less.
  • the thickness of these electrolyte membranes may be the same or different.
  • the first electrode 101 to the fourth electrode 104 and the intermediate electrode 120 may be made of a metal material, but at least one of them is made of a conductive oxide. It is preferable from the viewpoint of improving conductivity.
  • the oxide is one or more elements selected from the group consisting of MNO 3 (M is Ca, Sr, Ba, La, Pr and Y.
  • N is Ni, Ti, V, Zr, Having a perovskite-type structure represented by one or more elements selected from the group consisting of Cr, Mn, Fe, Co, Mo, Ru, Pd and Re) is a solid electrolyte membrane and an electrode. It is preferable from the viewpoint of further enhancing the oxide ion conductivity between the two.
  • An intermediate layer such as CeO 2 doped with Sm may be provided between the solid electrolyte membrane and the electrode.
  • the planar shape of the first electrode 101 to the fourth electrode 104 and the intermediate electrode 120 electrode various shapes such as a circle and a polygon can be adopted. Further, if necessary, a process for increasing the surface area may be performed by a known method. For example, the surface area can be increased by making the surface of the electrode uneven. This processing can further promote the movement of oxygen.
  • the thicknesses of the first electrode 101 to the fourth electrode 104 and the intermediate electrode 120 are not critical in the present invention, and may have enough strength to withstand the use of the oxygen sensor 1.
  • the thickness of these electrodes can generally be 0.01 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of these electrodes may be the same or different.
  • the annular wall portion 30 through which oxygen can permeate can be made of a material that is stable at the operating temperature of the oxygen sensor 1, for example, a ceramic material.
  • a ceramic material for example, alumina, zirconia, silica, zeolite and the like can be used.
  • the annular wall portion 30 is attached to the first membrane electrode assembly 10 and the second membrane electrode. It may be joined to the joining body 20.
  • the adhesive for example, a zirconia-based adhesive can be used.
  • FIGS. 5 to 8 Another embodiment of the oxygen sensor of the present invention will be described with reference to FIGS. 5 to 8.
  • points different from the embodiments shown in FIGS. 1 to 4 described above will be described, and the description of the embodiments shown in FIGS. 1 to 4 will be appropriately applied to points not particularly described.
  • FIGS. 5 to 8 the same members as those in FIGS. 1 to 4 are designated by the same reference numerals.
  • the oxygen sensor 1a shown in FIG. 5 includes a membrane electrode assembly 10a.
  • the membrane electrode assembly 10a includes a solid electrolyte membrane 100a having oxide ion conductivity, and a first electrode 101a and a second electrode 102a arranged on each surface of the solid electrolyte membrane 100a.
  • the membrane electrode assembly 10a acts as a concentration cell and also as an oxygen pump according to the switching of the switch 70.
  • the same material as that constituting the first solid electrolyte membrane 100 or the second solid electrolyte membrane 200 in the oxygen sensor 1 of the embodiment shown in FIGS. 1 and 3 can be used.
  • the first electrode 101a and the second electrode 102a the same materials as those constituting the first electrode 101 to the fourth electrode 104 and the intermediate electrode 120 in the oxygen sensor 1 of the embodiment shown in FIGS. 1 and 3 are used. Can be done. Further, the material constituting the first electrode 101a and the material constituting the second electrode 102a may be the same or different.
  • the electrode facing member 50 is arranged so as to face the second electrode 102a.
  • the electrode facing member 50 is represented as a flat plate-shaped member.
  • FIG. 5 shows a state in which the electrode facing member 50 and the second electrode 102a are in close contact with each other without a gap, but the present invention is not limited to this, and the electrode facing member 50 and the second electrode 102a are spaced apart from each other. It may be arranged.
  • An annular wall portion 31 is provided between the solid electrolyte membrane 100a and the electrode facing member 50.
  • the annular wall portion 31 is provided so as to surround the second electrode 102a.
  • the reference oxygen concentration space S is defined between the solid electrolyte membrane 100a and the electrode facing member 50 by the annular wall portion 31.
  • the reference oxygen concentration space S is defined by the annular wall portion 31, the solid electrolyte membrane 100a, the electrode facing member 50, and the second electrode 102a.
  • At least one of the electrode facing member 50 and the annular wall portion 31 is made of a material capable of allowing oxygen to pass through.
  • a material capable of allowing oxygen to pass through.
  • a porous material can be used. Therefore, the reference oxygen concentration space S communicates with the outside through at least one of the electrode facing member 50 and the annular wall portion 31. From the viewpoint of ease of manufacture when the oxygen sensor 1a is miniaturized, it is preferable that only the annular wall portion 31 is made of a material that allows oxygen to pass through.
  • annular wall portion 31 of the oxygen sensor 1a of the present embodiment does not necessarily have to allow oxygen to permeate as described above.
  • the annular wall portion 31 may be made of a material that can withstand the operating temperature of the oxygen sensor 1a.
  • the method of measuring the oxygen concentration in the test gas by the oxygen sensor 1a having the above configuration is as described below.
  • these members are arranged so that the first electrode 101a faces the atmosphere to be measured and the electrode facing member 50 faces the outside air (generally the atmosphere).
  • the entire oxygen sensor 1a is heated so that the solid electrolyte membrane 100a exhibits oxide ion conductivity.
  • the heating temperature can be the same as that of the embodiments shown in FIGS. 1, 3 and 4.
  • the second electrode 102a When oxide ion conductivity is exhibited in the solid electrolyte film 100a, the second electrode 102a is connected to the positive electrode of the DC power supply 40, and the first electrode 101a is connected to the negative electrode of the DC power supply 40. As a result, the oxygen pumping action is exhibited, and the oxygen gas contained in the atmosphere to be measured is reduced to oxide ions.
  • the oxide ion moves in the solid electrolyte membrane 100a and reaches the second electrode 102a.
  • the oxide ion that reaches the second electrode 102a emits an electron and changes into an oxygen gas.
  • the oxygen gas generated in this way is accumulated in the reference oxygen concentration space S.
  • the reference oxygen concentration space S is defined by a material that allows oxygen to permeate, and since the reference oxygen concentration space S communicates with the outside, the pressure in the reference oxygen concentration space S is excessive. Will not rise to.
  • the reference oxygen concentration in the reference oxygen concentration space S becomes the reference oxygen concentration in which the partial pressure of the oxygen gas is high while maintaining a certain pressure. It is preferable that the reference oxygen concentration is 100 vol% of oxygen from the viewpoint of high-precision measurement. The determination as to whether or not the oxygen concentration in the space S is 100 vol% is as described above.
  • the switch 70 connects the first electrode 101a and the second electrode 102a to the DC power supply 40 under that state. To release. At the same time, the electromotive force generated between the first electrode 101a and the second electrode 102a is measured by the voltmeter 60. After that, the oxygen concentration in the atmosphere to be measured facing the first electrode 101a is calculated according to the Nernst equation by the same procedure as that of the embodiment shown in FIG.
  • the oxygen sensor 1a of the present embodiment may have a high concentration of oxygen gas present in the reference oxygen concentration space S, so that the electrode facing member 50 is made high. It doesn't have to be strong.
  • FIG. 6 shows an example of the result of measuring the voltage between the first electrode 101a and the second electrode 102a using the oxygen sensor 1a.
  • the switch 70 when the switch 70 is turned on and the voltage of the DC power supply 40 is applied between the first electrode 101a and the second electrode 102a, the voltage of the DC power supply 40 is E 1 between the two electrodes. Is observed.
  • E 1 is the oxygen pumping action of oxygen gas is accumulated in the reference oxygen concentration space S, gradually increasing the concentration of the oxygen gas.
  • the oxygen sensor 1a does not measure the concentration of oxygen gas in the atmosphere to be measured.
  • the switch 70 When the oxygen gas is sufficiently accumulated in the reference oxygen concentration space S and the oxygen gas concentration is sufficiently increased, the switch 70 is turned off. From this point, the measurement of the concentration of oxygen gas in the atmosphere to be measured by the oxygen sensor 1a is started. Concentration of the voltage, i.e. electromotive force generated by the principle of a concentration cell is as shown in FIG. 6, lower than E 1, the oxygen gas in the measured atmosphere between the first electrode 101a and the second electrode 102a at this time Indicates the value corresponding to.
  • the electromotive force shown in FIG. 6 is an example when the concentration of oxygen gas in the atmosphere to be measured is constant.
  • the duration of measurement of the oxygen gas concentration by the oxygen sensor 1a depends on the change in the oxygen gas concentration in the reference oxygen concentration space S. Specifically, as long as the concentration of oxygen gas in the reference oxygen concentration space S is constant, highly accurate measurement can be continued.
  • the switch 70 is turned on again as shown in FIG. Then, oxygen gas is accumulated in the reference oxygen concentration space S. After that, the concentration of oxygen gas in the atmosphere to be measured is measured by the above procedure.
  • the oxygen sensor 1a of the present embodiment applies a voltage between the first electrode 101a and the second electrode 102a in a pulsed manner to supply and generate oxygen into the reference oxygen concentration space S.
  • the measurement of power is performed alternately.
  • the oxygen sensor 1a of the present embodiment is suitable for applying this to a portable device because the power saving of the sensor can be achieved by appropriately using the concentration cell and the oxygen pump action by switching the switch 70. Is.
  • the time during which the switch 70 is turned on is preferably 0.5 seconds or more and 10 seconds or less.
  • the duration during which the concentration of oxygen gas in the atmosphere to be measured can be measured by turning off the switch 70 is generally 3 seconds or more and 200 seconds or less.
  • the oxygen sensor 1b shown in FIG. 7 includes a membrane electrode assembly 10b.
  • the membrane electrode assembly 10b includes a solid electrolyte membrane 100b having oxide ion conductivity, a first electrode 101b and a second electrode 102b arranged on one surface of the solid electrolyte membrane 100b, and the other surface of the solid electrolyte membrane 100b. It is provided with an intermediate electrode 120b arranged in.
  • the membrane electrode assembly 10b includes a concentration cell and an oxygen pump in one structure thereof.
  • the same material as that constituting the first solid electrolyte membrane 100 or the second solid electrolyte membrane 200 in the oxygen sensor 1 of the embodiment shown in FIGS. 1 and 3 can be used.
  • the first electrode 101b, the second electrode 102b, and the intermediate electrode 120b are the same as the materials constituting the first electrode 101 to the fourth electrode 104 and the intermediate electrode 120 in the oxygen sensor 1 of the embodiment shown in FIGS. 1 and 3. Can be used. Further, the materials constituting the first electrode 101b, the second electrode 102b and the intermediate electrode 120b may be the same or different.
  • the electrode facing member 50 is arranged so as to face the intermediate electrode 120b.
  • the electrode facing member 50 is represented as a flat plate-shaped member. Further, in FIG. 7, a state in which the electrode facing member 50 and the intermediate electrode 120b are in close contact with each other without a gap is shown, but the present invention is not limited to this, and the electrode facing member 50 and the intermediate electrode 120b are arranged at intervals. It may have been done.
  • annular wall portion 31 is provided between the solid electrolyte membrane 100b and the electrode facing member 50.
  • the annular wall portion 31 is provided so as to surround the intermediate electrode 120b.
  • the reference oxygen concentration space S is defined between the solid electrolyte membrane 100b and the electrode facing member 50 by the annular wall portion 31.
  • the reference oxygen concentration space S is defined by the annular wall portion 31, the solid electrolyte membrane 100b, the electrode facing member 50, and the intermediate electrode 120.
  • the method of measuring the oxygen concentration in the test gas by the oxygen sensor 1b having the above configuration is as described below.
  • these members are arranged so that the first electrode 101b and the second electrode 102b face the atmosphere to be measured and the electrode facing member 50 faces the outside air (generally the atmosphere). Under this state, the entire oxygen sensor 1b is heated so that the solid electrolyte membrane 100b exhibits oxide ion conductivity.
  • these members may be arranged so that the first electrode 101b faces the atmosphere to be measured and the second electrode 102b and the electrode facing member 50 face the outside air (generally the atmosphere).
  • the intermediate electrode 120b is connected to the positive electrode of the DC power supply 40, and the second electrode 102b is connected to the negative electrode of the DC power supply 40.
  • the oxygen pumping action is exhibited, and the oxygen gas is accumulated in the reference oxygen concentration space S.
  • the reference oxygen concentration space S the reference oxygen concentration is in a state where the partial pressure of the oxygen gas is high while maintaining a certain pressure. Under this state, the electromotive force generated between the first electrode 101b and the intermediate electrode 120b is measured by the voltmeter 60. After that, the oxygen concentration in the atmosphere to be measured facing the first electrode 101b is calculated according to the Nernst equation by the same procedure as that of the embodiment shown in FIG.
  • the oxygen sensor 1b of the present embodiment has the advantages of improving the measurement accuracy and shortening the oxygen pumping time.
  • FIG. 8 shows another embodiment of the oxygen sensor shown in FIG. 7.
  • the intermediate electrode 120b provided in the oxygen sensor shown in FIG. 7 is divided into a third electrode 103b and a fourth electrode 104b and is independent of each other, as shown in FIG. It is different from the oxygen sensor 1.
  • the materials constituting the third electrode 103b and the fourth electrode 104b may be the same or different.
  • the third electrode 103b and the fourth electrode 104b are surrounded by an annular wall portion 31.
  • the reference oxygen concentration space S is formed by the annular wall portion 31, the solid electrolyte membrane 100b, the electrode facing member 50, the third electrode 103b, and the fourth electrode 104b. It is defined.
  • the method of measuring the oxygen concentration in the test gas by the oxygen sensor 1b having the above configuration is as described below. First, these members are arranged so that the first electrode 101b and the second electrode 102b face the atmosphere to be measured and the electrode facing member 50 faces the outside air. Under this state, the entire oxygen sensor 1b is heated so that the solid electrolyte membrane 100b exhibits oxide ion conductivity.
  • the fourth electrode 104b is connected to the positive electrode of the DC power supply 40, and the second electrode 102b is connected to the negative electrode of the DC power supply 40.
  • the oxygen pumping action is exhibited, and the oxygen gas is accumulated in the reference oxygen concentration space S.
  • the electromotive force generated between the first electrode 101b and the third electrode 103b is measured by the voltmeter 60.
  • the oxygen concentration in the atmosphere to be measured facing the first electrode 101b is calculated according to the Nernst equation by the same procedure as that of the embodiment shown in FIG. Also in this embodiment, since the concentration of oxygen gas in the atmosphere to be measured is measured in a state where the reference oxygen concentration is high, an advantageous effect that the measurement accuracy can be improved can be obtained.
  • the oxygen sensors 1, 1a, 1b of each of the above-described embodiments can be miniaturized and miniaturized due to their structures, and can significantly reduce power consumption. Therefore, oxygen sensors 1, 1a, 1b can be provided in the micromechanical electrical element (MEMS). This makes it possible to measure the concentration of oxygen gas in a minute space by mounting the oxygen sensor on a mobile device such as a personal computer or a mobile terminal.
  • MEMS micromechanical electrical element
  • an oxygen sensor capable of measuring the oxygen concentration in the test gas with high accuracy is provided. Further, according to the present invention, an oxygen sensor capable of miniaturization is provided.

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PCT/JP2020/009431 2019-03-22 2020-03-05 酸素センサ及びそれを具備する微小機械電気素子 WO2020195681A1 (ja)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56145342A (en) * 1980-04-14 1981-11-12 Toray Ind Inc Solid-electrolyte oximeter
JPS5797439A (en) * 1980-12-09 1982-06-17 Toray Ind Inc Oxygen sensor
JPS6024445A (ja) * 1983-07-20 1985-02-07 Toyota Motor Corp 空燃比検出器
JPS62129753A (ja) * 1985-11-29 1987-06-12 Yokogawa Electric Corp 固体電解質を用いた分析装置
US20090007637A1 (en) * 2007-07-06 2009-01-08 National Taiwan University Of Science & Technology Gas sensor
US20140318960A1 (en) * 2013-04-25 2014-10-30 Wisenstech Inc. Micromachined oxygen sensor and method of making the same
WO2016111110A1 (ja) * 2015-01-07 2016-07-14 三井金属鉱業株式会社 配向性アパタイト型酸化物イオン伝導体及びその製造方法
WO2017099963A1 (en) * 2015-12-09 2017-06-15 Honeywell International Inc. Electrochemical sensor and electronics on a ceramic substrate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56145342A (en) * 1980-04-14 1981-11-12 Toray Ind Inc Solid-electrolyte oximeter
JPS5797439A (en) * 1980-12-09 1982-06-17 Toray Ind Inc Oxygen sensor
JPS6024445A (ja) * 1983-07-20 1985-02-07 Toyota Motor Corp 空燃比検出器
JPS62129753A (ja) * 1985-11-29 1987-06-12 Yokogawa Electric Corp 固体電解質を用いた分析装置
US20090007637A1 (en) * 2007-07-06 2009-01-08 National Taiwan University Of Science & Technology Gas sensor
US20140318960A1 (en) * 2013-04-25 2014-10-30 Wisenstech Inc. Micromachined oxygen sensor and method of making the same
WO2016111110A1 (ja) * 2015-01-07 2016-07-14 三井金属鉱業株式会社 配向性アパタイト型酸化物イオン伝導体及びその製造方法
WO2017099963A1 (en) * 2015-12-09 2017-06-15 Honeywell International Inc. Electrochemical sensor and electronics on a ceramic substrate

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