WO2023162960A1 - 電気化学式酸素センサおよびその製造方法 - Google Patents

電気化学式酸素センサおよびその製造方法 Download PDF

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WO2023162960A1
WO2023162960A1 PCT/JP2023/006155 JP2023006155W WO2023162960A1 WO 2023162960 A1 WO2023162960 A1 WO 2023162960A1 JP 2023006155 W JP2023006155 W JP 2023006155W WO 2023162960 A1 WO2023162960 A1 WO 2023162960A1
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oxygen sensor
catalyst layer
positive electrode
oxygen
alloy
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PCT/JP2023/006155
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English (en)
French (fr)
Japanese (ja)
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北澤直久
渡辺光俊
岩波良治
大町あゆみ
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マクセル株式会社
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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
    • G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors

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  • This application relates to an electrochemical oxygen sensor that improves the reliability of measurements in gases with low oxygen concentrations, and a manufacturing method thereof.
  • Electrochemical oxygen sensors (hereinafter also referred to as oxygen sensors) have the advantage of being inexpensive, easy to use, and capable of operating at room temperature. It is used in a wide range of fields, such as oxygen concentration detection in medical equipment such as respirators.
  • an electrochemical oxygen sensor for example, one that has an aqueous electrolyte and uses Sn or an alloy thereof as a negative electrode is known (Patent Documents 1 and 2, etc.).
  • the electrochemical oxygen sensor In the electrochemical oxygen sensor, when oxygen flows into the interior, it is reduced at the positive electrode, and a metal elution reaction occurs at the negative electrode, generating a current between the positive electrode and the negative electrode according to the oxygen concentration. Therefore, for example, the current generated by the positive electrode reaction (reduction of oxygen at the positive electrode) is converted into voltage, and the oxygen concentration is obtained based on this value. Therefore, when the electrochemical oxygen sensor is placed in an oxygen-free environment, the positive electrode reaction as described above does not occur. should also be possible. In reality, however, in spite of being placed in an oxygen-free environment, several hours after the start of observation, measurement results may appear as if oxygen is present. For this reason, depending on the configuration of the oxygen sensor, it may be difficult to use it for measuring low-concentration oxygen gas.
  • the present application has been made in view of the above circumstances, and aims to provide an electrochemical oxygen sensor with improved reliability of measurement in a gas with a low oxygen concentration, and a method of manufacturing the same.
  • the electrochemical oxygen sensor of the present application includes a positive electrode, a negative electrode, an oxygen-permeable diaphragm, and an electrolytic solution composed of an aqueous solution, the negative electrode containing a metal that dissolves in the electrolytic solution, and the electrolytic solution having a pH 3 to 10 aqueous solution, the positive electrode includes a catalyst layer containing Au, one surface of the catalyst layer is in contact with the electrolyte, and the catalyst layer has at least the surface on the electrolyte side and contains Ag or an alloy of Ag.
  • the electrochemical oxygen sensor of the present application includes a first step of depositing Ag on the surface of a metal layer containing Au to form a catalyst layer, and placing the Ag-attached side of the catalyst layer on the electrolyte side. It can be manufactured by the manufacturing method of the present application including a second step of arranging and assembling the positive electrode.
  • an electrochemical oxygen sensor with improved reliability when measuring the oxygen concentration of a gas with a low oxygen content, and a method of manufacturing the same.
  • FIG. 1 is a cross-sectional view schematically showing an example of the electrochemical oxygen sensor of the present application.
  • FIG. 2 is a graph showing the characteristics evaluation test results of the electrochemical oxygen sensors of Examples 1-3 and Comparative Examples 1-2.
  • FIG. 3 is a graph showing the characteristic evaluation test results of the electrochemical oxygen sensors of Examples 4 to 5 and Comparative Example 3.
  • FIG. 1 is a cross-sectional view schematically showing an example of the electrochemical oxygen sensor of the present application.
  • FIG. 2 is a graph showing the characteristics evaluation test results of the electrochemical oxygen sensors of Examples 1-3 and Comparative Examples 1-2.
  • FIG. 3 is a graph showing the characteristic evaluation test results of the electrochemical oxygen sensors of Examples 4 to 5 and Comparative Example 3.
  • the electrochemical oxygen sensor of the present application includes a positive electrode, a negative electrode, a diaphragm that allows oxygen to pass through, and an electrolytic solution composed of an aqueous solution, the negative electrode contains a metal that dissolves in the electrolytic solution, and the electrolytic solution has a pH 3 to 10 aqueous solution, the positive electrode includes a catalyst layer containing Au, one surface of the catalyst layer is in contact with the electrolyte, and the catalyst layer has at least the surface on the electrolyte side has Ag or an alloy of Ag.
  • the positive electrode of the electrochemical oxygen sensor of the present application includes a catalyst layer containing Au, and the catalyst layer has Ag or an alloy of Ag on at least the surface on the side of the electrolyte that is in contact with the electrolyte. It is possible to improve the measurement accuracy when measuring the oxygen concentration of a gas with a low oxygen content.
  • the alloy of Ag is preferably an alloy of Au and Ag.
  • the other surface of the catalyst layer is arranged on the side of the diaphragm, and having Au or an alloy of Au on at least the surface on the side of the diaphragm is useful for prolonging the life of the oxygen sensor and for poisoning gases such as hydrogen sulfide. It is preferable from the aspect of preventing the influence of
  • the catalyst layer may be a laminate of a layer containing Ag or an alloy of Ag and a layer containing Au or an alloy of Au.
  • the content of Ag on the surface on the electrolyte solution side is higher than the content of Ag on the inside, in order to further enhance the effect of Ag.
  • the content of Ag in the total amount of metals in the catalyst layer is preferably 1 atomic % or more in order to further enhance its effect.
  • the content of Au in the total amount of metals in the catalyst layer is preferably 10 atomic % or more in order to further enhance its effect.
  • oxygen sensor an electrochemical oxygen sensor (hereinafter sometimes abbreviated as "oxygen sensor") in which the positive electrode catalyst layer is composed of Au is used in an oxygen-free environment, several hours after the start of use, it is determined whether oxygen exists or not.
  • a voltage rise such as The inventors of the present invention considered the reaction occurring inside the oxygen sensor and, as a result, thought that the voltage rise may occur for the following reasons.
  • the reaction represented by the following formula (1) occurs when oxygen is present.
  • the positive electrode does not react as shown in formula (1).
  • the positive electrode in a state where oxygen is not supplied to the positive electrode, the positive electrode is electrically connected to the negative electrode through the resistor, so that the negative electrode potential is applied.
  • the metal element is eluted from the negative electrode, and a deposition reaction of the eluted element occurs at the positive electrode (when the eluted element is Sn, the reaction represented by the following formula (2) or (3)) occurs between the positive and negative electrodes. It is believed that voltage is generated by the flow of current.
  • the catalyst layer containing the catalytic metal in the positive electrode has Ag or an alloy of Ag on at least the surface of the electrolyte solution side in contact with the electrolyte solution, so the oxygen sensor can be used in an oxygen-free environment.
  • the oxygen sensor of the present application can measure the concentration of oxygen in a wide concentration range, for example, it can be used in a gas with a low oxygen concentration, including an oxygen-free environment.
  • FIG. 1 is a cross-sectional view schematically showing a galvanic cell oxygen sensor, which is one embodiment of the electrochemical oxygen sensor of the present application.
  • the oxygen sensor 1 shown in FIG. 1 has a positive electrode 50 , a negative electrode 80 and an electrolytic solution 90 in a cylindrical container 20 with a bottom.
  • the container 20 is composed of a container body 21 that holds an electrolytic solution 90 inside, and a sealing lid 10 for fixing the protective film 40 , the diaphragm 60 and the positive electrode 50 to the opening of the container body 21 .
  • the sealing lid 10 is composed of a first sealing lid (inner lid) 11 and a second sealing lid (outer lid) 12 for fixing the first sealing lid 11 . and is attached to the container body 21 via an O-ring 30 .
  • a negative electrode 80 is arranged in a state of being immersed in the electrolytic solution inside the container main body 21 containing the electrolytic solution 90 , and a lead portion 81 is formed on the negative electrode 80 .
  • the positive electrode 50 is configured by laminating a catalyst layer (catalyst electrode) 51 and a positive electrode current collector 52 , and a lead wire 53 is attached to the positive electrode current collector 52 .
  • a hole 70 for passing the lead wire 53 attached to the positive electrode current collector 52 is provided in the lower part of the container body 21 holding the electrolytic solution 90 of the container 20 . Further, although not shown in FIG. 1 , in addition to the perforations 70 , perforations for supplying the electrolytic solution to the positive electrode 50 are also provided in the lower portion of the container body 21 .
  • a correction resistor 100 and a temperature compensating thermistor 110 are connected in series between the lead portion 81 of the negative electrode 80 and the lead wire 53 attached to the positive electrode current collector 52 , and housed inside the container body 21 .
  • a negative electrode terminal 82 is connected to a lead portion 81 of the negative electrode 80
  • a positive electrode terminal 54 is connected to a lead wire 53 attached to the positive electrode current collector 52 .
  • a diaphragm 60 that selectively allows permeation of oxygen and restricts the amount of permeation to match the battery reaction is arranged. is introduced into the positive electrode 50 through the diaphragm 60 .
  • a protective film 40 is arranged on the outer surface side of the diaphragm 60 to prevent dust, dust, water, and the like from adhering to the diaphragm 60 , and is fixed by the first sealing lid 11 .
  • the first sealing lid 11 functions as a pressing end plate for the protective film 40 , the diaphragm 60 and the positive electrode 50 .
  • a threaded portion is formed on the inner peripheral portion of the second sealing lid 12 so as to be screwed with the threaded portion formed on the outer peripheral portion of the opening of the container body 21 .
  • the first sealing lid 11 is pressed against the container body 21 via the O-ring 30, so that the protective film is formed while maintaining airtightness and liquidtightness.
  • the diaphragm 60 and the positive electrode 50 can be fixed to the container body 21 .
  • the negative electrode of the oxygen sensor uses a material containing a metal that dissolves in the electrolyte. can be suppressed, the negative electrode is preferably made of a material containing Sn or a Sn alloy, and more preferably made of a Sn alloy. Although this Sn or Sn alloy may contain a certain amount of impurities, it is desirable that the content of Pb is less than 1000 ppm in order to comply with the RoHS Directive.
  • Sn alloy specifically, general lead-free solder materials (Sn-3.0Ag-0.5Cu, Sn-3.5Ag, Sn-3.5Ag-0.75Cu, Sn-3.8Ag- 0.7Cu, Sn-3.9Ag-0.6Cu, Sn-4.0Ag-0.5Cu, Sn-1.0Ag-0.5Cu, Sn-1.0Ag-0.7Cu, Sn-0.3Ag- 0.7Cu, Sn-0.75Cu, Sn-0.7Cu-Ni-P-Ge, Sn-0.6Cu-Ni-P-GeSn-1.0Ag-0.7Cu-Bi-In, Sn-0.
  • solder materials Sn-3.0Ag-0.5Cu, Sn-3.5Ag, Sn-3.5Ag-0.75Cu, Sn-3.8Ag- 0.7Cu, Sn-3.9Ag-0.6Cu, Sn-4.0Ag-0.5Cu, Sn-1.0Ag-0.5Cu, Sn-1.0Ag-0.7Cu, Sn-0.3Ag- 0.7Cu,
  • the positive electrode of the oxygen sensor is composed of a catalyst layer containing a catalytic metal and a positive electrode current collector.
  • the catalyst which is the constituent material of the catalyst layer, is generally not particularly limited as long as it can generate current by electrochemical reduction of oxygen on the positive electrode. and silver (Ag), which has a function of preventing a positive electrode reaction in an oxygen-free environment. Au and Ag may be alloyed.
  • the catalyst layer using only Ag, which has the effect of preventing the positive electrode reaction in an oxygen-free environment.
  • the catalyst layer is composed only of Ag, the catalyst layer is easily affected by the poisoning gas, such as hydrogen sulfide, if the gas used to measure the oxygen concentration contains a poisoning gas. is limited, and problems arise in terms of practical use of the oxygen sensor.
  • the catalyst layer is formed using only Ag, the service life of the sensor is shortened compared to the catalyst layer containing Au, although the reason is not clear.
  • the catalyst layer is configured to contain Au, and Ag or an alloy of Ag is disposed at least on the surface of the catalyst layer on the electrolyte side that is in contact with the electrolyte.
  • the alloy of Ag an alloy of Au and Ag is preferably used from the viewpoint of the service life of the oxygen sensor.
  • the content of Ag in the total amount of metals in the catalyst layer is preferably 1 atomic % or more, and preferably 15 atomic % or more. It is more preferably 35 atomic % or more, particularly preferably 45 atomic % or more, and most preferably 45 atomic % or more.
  • the content of Ag in the total amount of metals in the catalyst layer is preferably 90 atomic % or less. It is preferably 60 atomic % or less, more preferably 40 atomic % or less, and most preferably 20 atomic % or less. That is, the content of Au in the total amount of metals in the catalyst layer is preferably 10 atomic % or more, more preferably 40 atomic % or more, particularly preferably 60 atomic % or more, and 80 atomic % or more. % or more is most preferable. Even if the composition of the catalyst layer is not uniform, the content of Ag and the content of Au may be adjusted so as to fall within the above range as a whole.
  • the catalyst layer can be entirely formed of a uniform alloy containing Au and Ag.
  • the surface in contact with the liquid is composed of Ag or an alloy of Ag (such as an alloy of Au and Ag), and the diaphragm side is composed of Au or an alloy of Au (Au and Ag having a smaller proportion of Ag than the surface in contact with the electrolyte). alloys, etc.).
  • the content of Ag in the catalyst layer increases from the surface on the side of the electrolyte toward the inside so that the content of Ag on the surface in contact with the electrolyte is higher than the content of Ag on the membrane side. It may decrease.
  • the Au content in the catalyst layer decreases from the diaphragm-side surface toward the inside so that the Au content on the membrane-side surface is higher than that on the electrolyte side. It is okay to continue.
  • a laminate of a layer containing Ag or an alloy of Ag and a layer containing Au or an alloy of Au may be used.
  • the thickness of the catalyst layer is thin, the effect can be sufficiently exhibited. is more preferred.
  • the catalyst layer can contain elements other than Au and Ag, such as metal elements having catalytic activity such as Fe, Co, Cu, Ni, Ru, Rh, Pd, Os, Ir, and Pt.
  • metal elements having catalytic activity such as Fe, Co, Cu, Ni, Ru, Rh, Pd, Os, Ir, and Pt.
  • the total content of metal elements other than Au and Ag is preferably 20 atomic % or less, more preferably 10 atomic % or less, of the total amount of metals in the catalyst layer. More preferably, it is particularly preferably 5 atomic % or less, and the catalyst layer may be composed only of Au and Ag.
  • the electrolyte of the oxygen sensor is composed of an aqueous solution, such as an aqueous solution containing acetic acid, potassium acetate and lead acetate, and an aqueous solution containing citric acid and citrate (alkali metal salt, etc.).
  • the aqueous solution that constitutes the electrolytic solution may contain various organic acids, inorganic acids, alkalis, salts thereof, etc. as necessary for the purpose of pH adjustment.
  • an aqueous solution containing a chelating agent as the electrolytic solution. It is presumed that the chelating agent has the effect of chelating the constituent metals of the negative electrode and dissolving them in the electrolytic solution (hereinafter referred to as the "chelating effect"), which may contribute to the extension of the life of the oxygen sensor. .
  • chelating agent refers to a molecule (including ions) having multiple coordination sites (coordination atoms) that form a coordinate bond with a metal ion, and forms a complex with the metal ion (complex It stabilizes metal ions by transformation), and can be contained in the electrolytic solution in the form of an acid or a salt thereof that generates the above molecules in the solvent constituting the electrolytic solution. Therefore, those having a single coordination site (coordination atom) such as phosphoric acid, acetic acid, carbonic acid and salts thereof with weak complexing power are not included in the "chelating agent” as used herein. .
  • Metal ions such as Sn 2+ eluted from the negative electrode during discharge are unstable in the electrolyte when the pH of the electrolyte is in the weakly acidic to weakly alkaline range, so they immediately form oxides and hydroxides on the negative electrode. , and may hinder the reaction of the negative electrode.
  • the electrolytic solution contains a chelating agent, the eluted metal ions are chelated and exist stably as complex ions, so that the reaction at the negative electrode can be prevented from being hindered.
  • a chelating agent generally has a chelating action and pH buffering ability (the ability to keep the pH of a solution almost constant even when a small amount of acid or base is added).
  • succinic acid, fumaric acid, maleic acid, citric acid, tartaric acid, glutaric acid, adipic acid, malic acid, malonic acid, aspartic acid, glutamic acid, ascorbic acid, salts thereof, etc. 1 type, or 2 or more types can be used.
  • citric acid As the chelating agent, from the viewpoint of enhancing the chelating action, it is more preferable to use those having high solubility in water, specifically citric acid, tartaric acid, glutamic acid and salts thereof.
  • the concentration of the chelating agent in the electrolytic solution is, for example, preferably 2.3 mol/L or more, more preferably 2.5 mol/L or more, and particularly preferably 2.7 mol/L or more. .
  • the electrolytic solution further contains ammonia to increase the molar concentration of the chelating agent in the electrolytic solution. By delaying, it is possible to prolong the life of the oxygen sensor.
  • the concentration of ammonia in the electrolytic solution is preferably 0.01 mol/L or more in order to facilitate the above-mentioned action of ammonia, and is preferably 0.1 mol/L or more in order to further enhance the above-mentioned action, and is preferably 1 mol/L. L or more is more preferable.
  • the upper limit of the concentration of ammonia in the electrolyte is not specified in particular, but since ammonia is a compound specified in Table 2 of Japan's "Poisonous and Deleterious Substances Control Law", from the viewpoint of safety , the concentration of ammonia in the electrolyte is preferably less than 10 mol/L.
  • the pH of the aqueous solution that constitutes the electrolyte is 3-10.
  • the oxygen sensor placed in an oxygen-free environment tends to cause a reaction in which the metal ions eluted from the negative electrode are deposited at the positive electrode. It is possible to prevent the problem of voltage rise of the oxygen sensor due to such a precipitation reaction.
  • a diaphragm on the outer surface of the positive electrode of the oxygen sensor to control the inflow of oxygen so that too much oxygen does not reach the catalyst electrode.
  • the diaphragm one that selectively allows oxygen to permeate and limits the permeation amount of oxygen gas is preferable.
  • the material and thickness of the membrane are not particularly limited, fluororesins such as polytetrafluoroethylene and tetrafluoroethylene-hexafluoropropylene copolymer; polyolefins such as polyethylene; and the like are usually used.
  • the diaphragm may be a porous membrane, a non-porous membrane, or a capillary-type membrane having pores formed with capillaries.
  • a protective film made of a porous resin film on the diaphragm.
  • the material and thickness of the protective film there are no particular restrictions on the material and thickness of the protective film as long as it can prevent dirt, dust, water, etc. from adhering to the diaphragm and has the function of permeating air (including oxygen).
  • a fluororesin such as polytetrafluoroethylene is used.
  • the container body 21 of the oxygen sensor 1 can be made of, for example, acrylonitrile-butadiene-styrene (ABS) resin.
  • the sealing lid 10 (the first sealing lid 11 and the second sealing lid 12) arranged at the opening of the container body 21 can be made of, for example, ABS resin, polypropylene, polycarbonate, fluororesin, or the like. can.
  • the oxygen sensor 1 can be kept air-tight and liquid-tight by deforming.
  • the material of the O-ring is not particularly limited, but nitrile rubber, silicone rubber, ethylene propylene rubber, fluororesin and the like are usually used.
  • the present application has been described by taking the galvanic cell oxygen sensor, which is one embodiment of the electrochemical oxygen sensor of the present application, as an example.
  • the oxygen sensor shown in FIG. 1 can be modified in various ways as long as it has the function of an oxygen sensor.
  • the electrochemical oxygen sensor of the present application can take the form of a constant potential oxygen sensor.
  • a constant potential oxygen sensor is a sensor that applies a constant voltage between a positive electrode and a negative electrode, and the applied voltage is set according to the electrochemical characteristics of each electrode and the type of gas to be detected.
  • the constant potential type oxygen sensor when an appropriate constant voltage is applied between the positive electrode and the negative electrode, the current flowing between them and the oxygen gas concentration have a proportional relationship.
  • the oxygen gas concentration of an unknown gas can be detected by measuring the voltage.
  • the electrochemical oxygen sensor of the present application can be preferably applied to applications in an oxygen-free environment, but can also be applied to the same applications as conventionally known electrochemical oxygen sensors.
  • the electrochemical oxygen sensor of the present application includes a first step of depositing Ag on the surface of a metal layer containing Au to form a catalyst layer, and placing the Ag-attached side of the catalyst layer on the electrolyte side. and a second step of arranging and assembling the positive electrode.
  • Ag attached to the surface of the metal layer containing Au may remain on the surface of the metal layer as it is without reacting with the underlying metal layer, or may be alloyed with the underlying metal layer (for example, Au) to An alloy of Ag (for example, an alloy of Au and Ag) may be formed on at least the surface of the layer.
  • the method for manufacturing an electrochemical oxygen sensor of the present application may further include a step of heat-treating the metal layer having Ag deposited on its surface in an inert atmosphere or a reducing atmosphere after the first step. This can promote the alloying of Au and Ag. By alloying Au and Ag, Ag can be stably retained in the catalyst layer.
  • Examples of methods for attaching Ag to the surface of a metal layer containing Au or further alloying Au and Ag include physical vapor deposition (PVD), chemical vapor deposition (CVD), reactive plasma chemical vapor deposition, and chemical vapor deposition. Phase deposition method (PACVD), ion plating method (IP), sputtering method and the like are exemplified. Moreover, the method of electrochemically depositing, such as electrodeposition, may be used.
  • the amount of Ag to be deposited is preferably such that the content of Ag in the total amount of metal in the catalyst layer is 1 atomic % or more in order to further enhance its effect.
  • the Ag content in the metal layer decreases from the surface toward the inside so that the Ag content on the surface is higher than the Ag content on the inside. good too.
  • Example 1 ⁇ Preparation of electrolytic solution> An electrolytic solution was prepared by dissolving citric acid, tripotassium citrate and ammonia in water. The molar concentrations in the electrolytic solution were citric acid: 2.5 mol/L, tripotassium citrate: 0.5 mol/L, and ammonia: 3.0 mol/L. The pH of this electrolytic solution was 4.30 at 25°C.
  • ⁇ Preparation of positive electrode catalyst layer> On the surface of the tetrafluoroethylene-hexafluoropropylene copolymer film that serves as the diaphragm, a metal film made of an alloy of Au and Ag with a thickness of about 70 nm was formed as a catalyst layer of the positive electrode by ion plating.
  • the sealing lid 10 (the first sealing lid 11 and the second sealing lid 12) was also made of ABS resin like the container body 21.
  • a porous polytetrafluoroethylene sheet was used as the protective film 40, and a tetrafluoroethylene-hexafluoropropylene copolymer film was used as the diaphragm 60, as described above.
  • the catalyst layer (catalyst electrode) 51 of the positive electrode 50 uses the previously prepared catalyst layer, and is arranged so that the surface 51a on the side opposite to the diaphragm 60 is in contact with the electrolytic solution.
  • a wire 53 made of titanium was used, and the positive electrode current collector 52 and the lead wire 53 were welded together.
  • the negative electrode 80 was made of a Sn--Sb alloy (Sb content: 5% by mass).
  • a correction resistor 100 and a temperature compensating thermistor 110 are connected in series.
  • the oxygen concentration can be detected from the output voltage.
  • the first sealing lid 11, the O-ring 30, the protective film 40 made of polytetrafluoroethylene sheet, the diaphragm 60 made of tetrafluoroethylene-hexafluoropropylene copolymer, the catalyst electrode 51, and the positive electrode current collector 52 are pressed by screwing the container main body 21 and the second sealing lid 12 to maintain a good sealing state.
  • Example 1 In the same manner as in Example 1, except that instead of the metal film made of an alloy of Au and Ag, a metal film made of only Au having a thickness of about 70 nm prepared by an ion plating method was used as the positive electrode catalyst layer. Assembled the oxygen sensor.
  • Example 2 In the same manner as in Example 1, except that instead of the metal film made of an alloy of Au and Ag, a metal film made of only Ag having a thickness of about 70 nm prepared by an ion plating method was used as the positive electrode catalyst layer. Assembled the oxygen sensor.
  • An oxygen sensor was assembled in the same manner as in Example 1, except that the catalyst layer of the positive electrode was used and the side on which Ag was laminated was placed in contact with the electrolytic solution.
  • Example 5 A laminated film composed of an Au layer and an Ag layer was produced as a positive electrode catalyst layer in the same manner as in Example 4, except that the thickness of the Ag film laminated on the surface of the Au metal film was changed to about 30 nm.
  • An oxygen sensor was assembled in the same manner as in Example 1, except that the catalyst layer of the positive electrode was used and the side on which Ag was laminated was placed in contact with the electrolytic solution.
  • Example 3 An oxygen sensor was assembled in the same manner as in Example 1, except that a metal film of Au having a thickness of about 60 nm formed by an ion plating method was used as it was as the catalyst layer of the positive electrode.

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PCT/JP2023/006155 2022-02-22 2023-02-21 電気化学式酸素センサおよびその製造方法 WO2023162960A1 (ja)

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Publication number Priority date Publication date Assignee Title
WO2025177606A1 (ja) * 2024-02-20 2025-08-28 マクセル株式会社 電気化学式酸素センサ

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006194708A (ja) * 2005-01-13 2006-07-27 Gs Yuasa Corporation:Kk 電気化学式酸素センサ
JP2017067596A (ja) * 2015-09-30 2017-04-06 株式会社Ｇｓユアサ 酸素センサ
JP2018059720A (ja) * 2016-09-30 2018-04-12 株式会社Ｇｓユアサ ガルバニ電池式酸素センサ
WO2020079769A1 (ja) * 2018-10-17 2020-04-23 マクセル株式会社 電気化学式酸素センサ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006194708A (ja) * 2005-01-13 2006-07-27 Gs Yuasa Corporation:Kk 電気化学式酸素センサ
JP2017067596A (ja) * 2015-09-30 2017-04-06 株式会社Ｇｓユアサ 酸素センサ
JP2018059720A (ja) * 2016-09-30 2018-04-12 株式会社Ｇｓユアサ ガルバニ電池式酸素センサ
WO2020079769A1 (ja) * 2018-10-17 2020-04-23 マクセル株式会社 電気化学式酸素センサ

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025177606A1 (ja) * 2024-02-20 2025-08-28 マクセル株式会社 電気化学式酸素センサ

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