WO2022113389A1 - 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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Publication number
WO2022113389A1
WO2022113389A1 PCT/JP2021/009326 JP2021009326W WO2022113389A1 WO 2022113389 A1 WO2022113389 A1 WO 2022113389A1 JP 2021009326 W JP2021009326 W JP 2021009326W WO 2022113389 A1 WO2022113389 A1 WO 2022113389A1
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Prior art keywords
oxygen sensor
positive electrode
negative electrode
electrolytic solution
electrochemical oxygen
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PCT/JP2021/009326
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English (en)
French (fr)
Japanese (ja)
Inventor
渡辺光俊
北澤直久
岩波良治
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Maxell Ltd
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Maxell Ltd
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Priority to US18/253,841 priority Critical patent/US12529674B2/en
Priority to JP2022565034A priority patent/JP7555426B2/ja
Priority to EP21897369.1A priority patent/EP4253949B1/en
Priority to CN202180091401.0A priority patent/CN116710767B/xx
Publication of WO2022113389A1 publication Critical patent/WO2022113389A1/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
    • G01N27/413—Concentration cells using liquid electrolytes measuring currents or voltages in voltaic cells
    • 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
    • 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
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/304—Gas permeable electrodes

Definitions

  • the present invention relates to an electrochemical oxygen sensor having improved measurement reliability in a gas having a low oxygen concentration, and a method for manufacturing the same.
  • the electrochemical oxygen sensor (hereinafter, also referred to as an oxygen sensor) has the advantages of being inexpensive, easy, and capable of operating at room temperature. It is used in a wide range of fields such as detection of oxygen concentration in medical devices such as respirators.
  • an electrochemical oxygen sensor for example, one having an aqueous solution-based electrolytic solution and using Sn or an alloy thereof for the negative electrode is known (Patent Documents 1, 2, etc.).
  • the electrochemical oxygen sensor when oxygen enters the inside, it is reduced at the positive electrode, and a metal elution reaction occurs at the negative electrode, so that a current corresponding to the oxygen concentration is generated between the positive electrode and the negative electrode. Therefore, for example, the current generated by the positive electrode reaction (reduction of oxygen at the positive electrode) is converted into a 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 above-mentioned positive reaction does not occur, so that the above-mentioned current does not originally occur and the oxygen concentration is zero. Should also be possible.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an electrochemical oxygen sensor having improved measurement reliability in a gas having a low oxygen concentration, and a method for manufacturing the same.
  • the electrochemical oxygen sensor of the present invention contains an electrolytic solution composed of a positive electrode, a negative electrode, and an aqueous solution, and the negative electrode contains a metal containing an element M selected from Sn and Ni as a main component, and the electrolytic solution.
  • the positive electrode contains a catalyst layer containing a catalyst metal, and the catalyst layer includes a surface layer containing the element M on a surface in contact with the electrolytic solution. ..
  • the electrochemical oxygen sensor of the present invention comprises a positive electrode containing a catalyst layer containing a catalytic metal, a negative electrode containing a metal containing an element M selected from Sn and Ni as a main component, and an aqueous solution having a pH of 3 to 10.
  • an electrochemical oxygen sensor having improved reliability when measuring the oxygen concentration of a gas having a low oxygen content, and a method for manufacturing the same.
  • FIG. 1 is a graph showing a change in output voltage when an electrochemical oxygen sensor having a negative electrode containing Sn is used in an oxygen-free environment.
  • FIG. 2 is a cross-sectional view schematically showing an example of the electrochemical oxygen sensor of the present invention.
  • FIG. 3 is a graph showing the characteristics evaluation test results of the electrochemical oxygen sensors of Examples 1 and 2 and Comparative Example 1.
  • oxygen sensor an electrochemical oxygen sensor
  • oxygen sensor oxygen sensor
  • oxygen sensor oxygen-free environment
  • a voltage rise is observed as if oxygen is present for a certain period of time. Further, it has been clarified by the study of the present inventor that the voltage rise disappears when the measurement is continued. As a result of examining the reaction occurring inside the oxygen sensor, the present inventors considered that the voltage increase may occur due to the following reasons.
  • the voltage rise occurs after a certain period of time, but after a certain period of time, the voltage rise is no longer observed. During this period, it is considered that the reaction of precipitating Sn of the formula (3) or the formula (4) is proceeding at the positive electrode instead of the reaction of generating hydrogen of the formula (2), and the potential of the positive electrode gradually decreases. When it becomes equal to the potential of the negative electrode, the current becomes zero, the precipitation of Sn at the positive electrode is completed, and the abnormality of the voltage of the oxygen sensor does not occur.
  • the present inventors can prevent the reaction at the positive electrode by forming a layer containing the element M contained in the negative electrode in advance on the surface of the catalyst layer in contact with the electrolytic solution. , I thought that it would be possible to improve the reliability when measuring a gas with a low oxygen concentration.
  • the surface of the catalyst layer containing the catalyst metal in the positive electrode, which is in contact with the electrolytic solution, is contained in the metal contained in the negative electrode, that is, the metal containing the element M selected from Sn and Ni as the main component. Since a layer containing the same element as the element M is formed, it is necessary to prevent a voltage increase due to a precipitation reaction of metal ions eluted from the negative electrode at the positive electrode when the oxygen sensor is used in an oxygen-free environment. Is possible.
  • the oxygen sensor of the present invention can measure the oxygen concentration in a wide concentration range, for example, it can be used in a gas having a low oxygen concentration including in an oxygen-free environment.
  • the metal element is oxidized and exists in the state of an oxide or the like at least on the surface layer portion of the surface of the catalyst layer in contact with the electrolytic solution.
  • the "surface layer” formed on the surface of the catalyst layer in contact with the electrolytic solution and containing the same element as the element (Sn or Ni) which is the main component of the metal contained in the negative electrode is a single layer of the element.
  • a layer of the alloy of the element for example, a layer of an alloy of the catalyst metal and the element, a layer of an oxide of the element, and the like are also included.
  • metal containing the element M as the main component and the “metal containing the element M as the main component” as used herein mean a metal having an element M content of more than 50% by mass.
  • the oxygen sensor of the present invention will be described with reference to the galvanic cell type oxygen sensor, which is an example of a preferred embodiment.
  • FIG. 2 is a cross-sectional view schematically showing a galvanic cell type oxygen sensor, which is an embodiment of the electrochemical oxygen sensor of the present invention.
  • the oxygen sensor 1 shown in FIG. 2 has a positive electrode 50, a negative electrode 80, and an electrolytic solution 90 in a bottomed cylindrical container 20.
  • the container 20 is composed of a container main body 21 that holds the 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 main 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 oxygen is contained in the oxygen sensor 1. It has a through hole 120 for taking in, and is attached to the container body 21 via an O-ring 30.
  • the negative electrode 80 is arranged in a state of being immersed in the electrolytic solution inside the container main body 21 that houses the electrolytic solution 90, and the lead portion 81 is formed in 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 perforation 70 for passing the lead wire 53 attached to the positive electrode current collector 52 is provided in the lower part of the container main body 21 that holds the electrolytic solution 90 in the container 20.
  • a perforation for supplying the electrolytic solution to the positive electrode 50 is provided in the lower part of the container main body 21 in addition to the perforation 70.
  • 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 are housed inside the container body 21. .. Further, the negative electrode terminal 82 is connected to the lead portion 81 of the negative electrode 80, and the positive electrode terminal 54 is connected to the lead wire 53 attached to the positive electrode current collector 52, and each of them is outside the container body 21. It is derived from.
  • a diaphragm 60 that selectively allows oxygen to permeate and limits the amount of permeation to match the battery reaction is arranged, and oxygen from the through hole 120 provided in the sealing lid 10 is arranged. Is introduced into the positive electrode 50 through the diaphragm 60. Further, a protective film 40 for preventing dust, dust, water, etc. from adhering to the diaphragm 60 is arranged on the outer surface side of 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 screw portion is formed on the inner peripheral portion of the second sealing lid 12 so as to be screwed with the screw portion formed on the outer peripheral portion of the opening of the container main body 21. Then, by tightening the sealing lid 10 with screws, the first sealing lid 11 is pressed against the container body 21 via the O-ring 30, so that the protective film is maintained in an airtightness and a liquidtightness. 40, the diaphragm 60 and the positive electrode 50 can be fixed to the container body 21.
  • the negative electrode of the oxygen sensor is a simple substance of either Sn or Ni, or an alloy of the above elements [one of Sn and Ni is the main component (content in the alloy exceeds 50% by mass). Alloy] is used.
  • the elemental substance or its alloy may contain a certain amount of impurities, but the content of Pb is preferably less than 1000 ppm in order to comply with the RoHS Directive.
  • Na, Zn, Ca, Ge, In, Ni, Co and the like may be an alloy containing a metal element.
  • Sn alloy 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.
  • Ni alloys that can be used for the negative electrode include Ni—V alloys, Ni—Cr alloys, Ni—Si alloys, Ni—Al alloys, Ni—Ti alloys, Ni—Mo alloys, and Ni—Mn alloys from the viewpoint of corrosion resistance. Examples thereof include Ni—Zn alloys, Ni—Sn alloys, Ni—Cu alloys, Ni—Co alloys, and Ni—Fe alloys, but alloys containing metal elements other than the above may be used.
  • Ni alloy examples include Ni66-Cu29-Al3, Ni63-Cu30-Si4, Ni63-Cu30-Si3, Ni62-Mo28-Fe5, Ni68-Mo28-Fe2-Cr1-Co1, and Ni57-Mo17-Cr16-. Alloys such as Fe4-W3 and Ni22-Cr9-Mo0.6-W18.5-Fe1.5-Co0.6 can be preferably used.
  • the negative electrode is preferably made of Sn or Sn alloy because it is less likely to corrode in an electrolytic solution consisting of an aqueous solution having a pH of 3 to 10 and can suppress the generation of hydrogen in the positive electrode in an oxygen-free environment. , Sn alloy is more preferred.
  • a positive electrode composed of a catalyst layer containing a catalyst metal and a positive electrode current collector is used as the positive electrode of the oxygen sensor.
  • the catalyst which is a constituent material of the catalyst layer is not particularly limited as long as it can generate an electric current by the reduction of electrochemical oxygen on the positive electrode, but gold (Au), silver (Ag), platinum (Pt), and the like.
  • the surface layer may be composed of only the same element (including unavoidable impurities) as the element M which is the main component of the metal contained in the negative electrode, and is the same element as the element M which is the main component of the metal contained in the negative electrode. It may be composed of an alloy containing the above as a main component [the ratio of the element M in the alloy exceeds 50% by mass].
  • the alloying elements include, for example, various metal elements exemplified above as those which can be contained when the negative electrode is composed of the alloy of the element M. Can be mentioned.
  • the amount of element M [the same element as element M contained in the negative electrode] per unit area is used from the viewpoint of better ensuring the effect of preventing unnecessary positive reaction in the oxygen-free environment in the oxygen sensor. It is preferably 10 ⁇ g / cm 2 or more, and more preferably 50 ⁇ g / cm 2 or more. Further, the amount of the element M in the surface layer per unit area is preferably 10 mg / cm 2 or less, and more preferably 4 mg / cm 2 or less so as not to inhibit the action of the catalytic metal.
  • An aqueous solution composed of an aqueous solution is used as the electrolytic solution of the oxygen sensor, for example, an aqueous solution containing acetic acid, potassium acetate and lead acetate, an aqueous solution containing citric acid and a citrate (alkali metal salt, etc.), and the like.
  • An acidic aqueous solution containing a carboxylic acid or a salt thereof; an alkaline aqueous solution such as a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution; can be used.
  • the aqueous solution constituting the electrolytic solution may contain various organic acids, inorganic acids and alkalis, if necessary, for the purpose of adjusting the pH.
  • chelating agent has an action of chelating the constituent metal (element M) of the negative electrode and dissolving it in the electrolytic solution (hereinafter referred to as "chelating action"), which contributes to extending the life of the oxygen sensor. It is thought to get.
  • the "chelating agent" as used herein has a molecule (including an ion) having a plurality of functional groups that coordinate with a metal ion, and forms (complexes) a complex with the metal ion to form a metal ion.
  • Metal ions such as Sn 2+ eluted from the negative electrode during discharge are unstable in the electrolytic solution when the pH of the electrolytic solution is in the range of weakly acidic to weakly alkaline, so they are immediately placed on the negative electrode as oxides or hydroxides. It may precipitate in the negative electrode and hinder the reaction of the negative electrode.
  • the eluted metal ions are chelated and stably exist as complex ions, so that it is possible to prevent the reaction of the negative electrode from being inhibited.
  • Chelating agents generally have a chelating effect and a 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), as a specific example thereof.
  • a 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.
  • One kind or two or more kinds can be used.
  • citric acid As the chelating agent, those having high solubility in water from the viewpoint of enhancing the chelating action, specifically, citric acid, tartaric acid, glutamic acid and salts thereof are more preferable.
  • 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 oxide of the metal is generated and the negative electrode becomes inactive, which may impair the life of the oxygen sensor.
  • the liquid contains a chelating agent, the effect of extending the life of the oxygen sensor may be limited.
  • 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 preferably 0.1 mol / L or more in order to further enhance the above-mentioned action, and is 1 mol / L. It is more preferably L or more.
  • the upper limit of the concentration of ammonia in the electrolytic solution is not particularly specified, but since ammonia is a compound specified in Appendix 2 of the "Poisonous and Deleterious Substances Control Law" in Japan, from the viewpoint of safety.
  • the concentration of ammonia in the electrolytic solution is preferably less than 10% by mass.
  • the pH of the aqueous solution constituting the electrolytic solution is 3 to 10.
  • a reaction in which element M is slightly eluted from the negative electrode and precipitated at the positive electrode is likely to occur. If there is, it is possible to prevent the problem of voltage rise of the oxygen sensor due to such a precipitation reaction.
  • a diaphragm for controlling the intrusion of oxygen on the outer surface of the positive electrode of the oxygen sensor so that the amount of oxygen reaching the catalyst electrode does not become too large.
  • the material and thickness of the diaphragm are not particularly limited, but usually fluororesins such as polytetrafluoroethylene and tetrafluoroethylene-hexafluoropropylene copolymer; polyolefins such as polyethylene; and the like are used.
  • a porous membrane, a non-porous membrane, and a membrane having pores in which capillaries are formed which is called a capillary type, can be used.
  • a protective film made of a porous resin film on the diaphragm.
  • the material and thickness of the protective film are not particularly limited, but usually Fluororesin such as polytetrafluoroethylene is used.
  • the container body 21 of the oxygen sensor 1 can be made of, for example, an acrylonitrile-butadiene-styrene (ABS) resin.
  • ABS acrylonitrile-butadiene-styrene
  • the sealing lid 10 (first sealing lid 11 and second sealing lid 12) arranged in the opening of the container main body 21 may be made of, for example, ABS resin, polypropylene, polycarbonate, fluororesin or the like. can.
  • the O-ring 30 interposed between the container body 21 of the container 20 and the sealing lid 10 (first sealing lid 11) is pressed by screw tightening between the container body 21 and the second sealing lid 12.
  • the material of the O-ring is not particularly limited, but nitrile rubber, silicone rubber, ethylene propylene rubber, fluororesin, or the like is usually used.
  • the present invention has been described by taking a galvanized battery type oxygen sensor, which is an embodiment of the electrochemical oxygen sensor of the present invention, as an example, but the electrochemical oxygen sensor of the present invention is not limited to the above embodiment. , Various changes are possible within the scope of its technical idea. Further, the oxygen sensor shown in FIG. 2 can be changed in various designs as long as it has a function as an oxygen sensor and the above-mentioned oxygen supply path.
  • the electrochemical oxygen sensor of the present invention can also take the form of a constant potential oxygen sensor.
  • the constant potential oxygen sensor is a sensor that applies a constant voltage between the positive electrode and the negative electrode, and the applied voltage is set according to the electrochemical characteristics of each electrode and the gas type to be detected.
  • a constant potential 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 invention has a positive electrode having a surface layer formed in advance on the surface of a catalyst layer (catalyst electrode) by a vapor deposition method, a plating method, or the like, and a metal containing element M selected from Sn and Ni as main components. It can be produced by a method of assembling using a negative electrode containing the above and an electrolytic solution consisting of an aqueous solution having a pH of 3 to 10.
  • an electrochemical oxygen sensor can also be manufactured by a manufacturing method including a step of precipitating the element M from the electrolytic solution on the surface to form the surface layer.
  • the step of forming the surface layer on the positive electrode in advance can be omitted, it is possible to further increase the productivity of the electrochemical oxygen sensor.
  • the time for conducting the positive electrode and the negative electrode to deposit the element M on the surface of the main body of the positive electrode may be, for example, 50 to 150 hours.
  • the electrochemical oxygen sensor of the present invention can be preferably applied to applications used in an oxygen-free environment, but can also be applied to the same applications as conventionally known electrochemical oxygen sensors.
  • Example 1 Preparation of electrolyte> An electrolytic solution was prepared by dissolving citric acid, tripotassium citrate and ammonia in water. The molar concentration in the electrolytic solution was citric acid: 2.5 mol / L, tripotassium citrate: 0.5 mol / L, and ammonia: 3.0 mol / L. The pH of this electrolyte was 4.30 at 25 ° C.
  • the sealing lid 10 (first sealing lid 11 and second sealing lid 12) was also made of ABS resin in the same manner as the container body 21. Further, a porous polytetrafluoroethylene sheet was used for the protective film 40, and a tetrafluoroethylene-hexafluoropropylene copolymer film was used for the diaphragm 60.
  • the catalyst layer (catalyst electrode) 51 of the positive electrode 50 is made of gold, the positive electrode current collector 52 and the lead wire 53 are made of titanium, and the positive electrode current collector 52 and the lead wire 53 are welded and integrated. It became.
  • the negative electrode 80 was made of a Sn—Sb alloy (Sb content: 5% by mass).
  • a correction resistance 100 and a temperature compensating thermista 110 are connected in series between the lead wire 53 of the positive electrode and the lead portion 81 of the negative electrode, and further, the lead wire 53 of the positive electrode and the lead portion 81 of the negative electrode are connected to the positive electrode.
  • the positive electrode current collector 52 is pressed by screwing the container body 21 and the second sealing lid 12 to maintain a good sealing state.
  • Example 2 A Sn layer (surface layer, the amount of Sn per unit area is 150 ⁇ g / cm 2 ) is formed on one side of the catalyst layer (catalyst electrode) of the positive electrode by a plating method, and the same as in Example 1 except that this positive electrode is used. And assembled the oxygen sensor.
  • Comparative Example 1 The oxygen sensor assembled in the same manner as in Example 1 was used as the oxygen sensor of Comparative Example 1 without forming the above-mentioned surface layer.
  • the present application can be implemented in a form other than the above as long as it does not deviate from the purpose.
  • the embodiments disclosed in the present application are examples, and the present invention is not limited thereto.
  • the scope of the present application shall be construed in preference to the description of the appended claims over the description of the specification described above, and all changes within the scope of the claims shall be included in the scope of the claims. It is something that can be done.

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PCT/JP2021/009326 2020-11-25 2021-03-09 電気化学式酸素センサおよびその製造方法 Ceased WO2022113389A1 (ja)

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Application Number Priority Date Filing Date Title
US18/253,841 US12529674B2 (en) 2020-11-25 2021-03-09 Electrochemical oxygen sensor and method for manufacturing the same
JP2022565034A JP7555426B2 (ja) 2020-11-25 2021-03-09 電気化学式酸素センサおよびその製造方法
EP21897369.1A EP4253949B1 (en) 2020-11-25 2021-03-09 Electrochemical oxygen sensor and method for producing same
CN202180091401.0A CN116710767B (en) 2020-11-25 2021-03-09 Electrochemical oxygen sensor and method for manufacturing the same

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JP2020195501 2020-11-25
JP2020-195501 2020-11-25

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GB1044456A (en) 1965-03-09 1966-09-28 Mullard Ltd Improvements in apparatus for oxygen determination
US4681673A (en) 1984-10-29 1987-07-21 General Electric Company Portable oxygen sensor with shortened break-in time
KR890000606B1 (ko) 1985-07-25 1989-03-21 텔레딘 인더스트리 인코오퍼레이티드 가스분석기
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Publication number Priority date Publication date Assignee Title
JPS548591A (en) * 1977-06-21 1979-01-22 Japan Storage Battery Co Ltd Oxygen concentration meter
US4705617A (en) * 1983-05-06 1987-11-10 Sensormedics Corporation Apparatus for deplating cutaneous gas sensors
JPS61112954A (ja) * 1984-10-29 1986-05-30 ゼネラル・エレクトリツク・カンパニイ ならし運転時間の短かいポータブル酸素センサ
JP2006194708A (ja) 2005-01-13 2006-07-27 Gs Yuasa Corporation:Kk 電気化学式酸素センサ
JP2015505358A (ja) * 2011-09-29 2015-02-19 ブリガム・ヤング・ユニバーシティＢｒｉｇｈａｍ Ｙｏｕｎｇ Ｕｎｉｖｅｒｓｉｔｙ 鉛フリー酸素センサ
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US12529674B2 (en) 2026-01-20
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EP4253949B1 (en) 2025-01-29
JP7555426B2 (ja) 2024-09-24

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