WO2022079925A1 - Capteur de concentration de gaz hydrogène de pile à combustible - Google Patents

Capteur de concentration de gaz hydrogène de pile à combustible Download PDF

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Publication number
WO2022079925A1
WO2022079925A1 PCT/JP2020/046165 JP2020046165W WO2022079925A1 WO 2022079925 A1 WO2022079925 A1 WO 2022079925A1 JP 2020046165 W JP2020046165 W JP 2020046165W WO 2022079925 A1 WO2022079925 A1 WO 2022079925A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen gas
electrode
concentration
gas concentration
sensor
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PCT/JP2020/046165
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English (en)
Japanese (ja)
Inventor
修治 原田
克己 高木
洋司 結城
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株式会社新潟Tlo
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Application filed by 株式会社新潟Tlo filed Critical 株式会社新潟Tlo
Publication of WO2022079925A1 publication Critical patent/WO2022079925A1/fr

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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
    • 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
    • G01N27/416—Systems

Definitions

  • the present invention relates to a hydrogen gas concentration sensor for a fuel cell.
  • the conventional hydrogen gas concentration sensor is based on the detection method of semiconductor type, ionization type, combustion type, etc. These measurement principles are “extensive physical quantities” such as “carrier concentration (semiconductor type)", “ion concentration (ionization type)", or “heat of reaction (burning type or burning and measuring its water vapor pressure)”. "The amount of hydrogen is detected by an indirect detection method, and they are converted into an electrical quantity to be used as a sensor. Therefore, it took time to detect the hydrogen gas, and it took 100 seconds or more for the slow one.
  • a hydrogen gas concentration sensor for a fuel cell can detect hydrogen gas in the entire concentration range from low concentration to high concentration, and it is indispensable that the time required for detection is short.
  • Patent Document 1 discloses a hydrogen gas concentration sensor in which a detection electrode and a reference electrode are appropriately selected from nickel, titanium, copper iron, aluminum, alloys containing these, and organic conductive materials.
  • the hydrogen gas concentration sensor can detect the hydrogen gas concentration under high concentration, it is difficult to detect the hydrogen gas concentration under low concentration. Further, there is a problem that the response time is long and the time required for detection becomes long.
  • An object of the present invention is to provide a novel hydrogen gas concentration sensor for a fuel cell capable of detecting hydrogen gas from a low concentration to a high concentration, having an excellent response speed, and shortening the detection time.
  • the present invention is as shown below.
  • a first electrode and a second electrode are provided, and a first solid electrolyte that comes into contact with these electrodes is provided, and the first electrode is H 2 ( ⁇ )
  • Material sample ( The first electrode material having a standard electromotive force value of 0.8 V or more in the cell configured with +) is included, and the second electrode has a standard electromotive force value of less than 0.8 V in the cell having the same configuration.
  • a low-concentration hydrogen gas concentration sensor including a second electrode material indicating a value, a third electrode and a fourth electrode, and a second solid electrolyte in contact with these electrodes are provided, and the third electrode is H 2 (.
  • the standard electromotive force value of the cell composed of the substance sample (+) is 0.8 V or more, and the third electrode material having hydrogen absorption property is included.
  • the fourth electrode comprises a high concentration hydrogen gas concentration sensor including a fourth electrode material having a standard electromotive force value of less than 0.8 V in the cell having the same configuration. Hydrogen gas concentration sensor for.
  • the first electrode material is characterized by containing at least one of platinum, a platinum alloy and a material containing them, and the third electrode is characterized by containing at least one of palladium, a palladium alloy and a material containing them.
  • the second electrode material and the fourth electrode material are nickel, nickel alloy, titanium, titanium alloy, copper, copper alloy, iron, iron alloy, aluminum, aluminum alloy, organic conductive material, and materials containing these.
  • the hydrogen gas concentration sensor for a fuel cell according to (2) which comprises at least one.
  • the low-concentration hydrogen gas concentration sensor is used in an environment where the hydrogen gas concentration is less than 10% by volume
  • the high-concentration hydrogen gas concentration sensor is used in an environment where the hydrogen gas concentration is 10% by volume or more.
  • a novel hydrogen gas concentration sensor for a fuel cell that can detect hydrogen gas from a low concentration to a high concentration, has an excellent response speed, and can shorten the detection time.
  • FIG. 1 is a schematic configuration diagram of a fuel cell system according to the present embodiment
  • FIG. 2 is a schematic configuration diagram of a hydrogen gas concentration sensor used in the fuel cell system shown in FIG.
  • the fuel cell 10 of the fuel cell system in the present embodiment has a fuel electrode 11, an air electrode 12, and an electrolyte 13 sandwiched between these electrodes.
  • the fuel cell 10 can be configured from any shape such as a solid polymer fuel cell, a phosphoric acid fuel cell, a molten carbonate fuel cell, a solid oxide fuel cell, and the like.
  • the fuel cell 10 is arranged inside the case 16, and a low-concentration hydrogen gas sensor 20 is arranged outside the case 16 under a low-concentration hydrogen gas environment, for example, in the discharge pipe 121 of the air electrode 12, and has a high concentration.
  • a high-concentration hydrogen gas sensor 30 and a low-concentration hydrogen gas sensor 20 are arranged inside the case 16 under a hydrogen gas environment, for example, in the discharge pipe 111 of the fuel electrode 11.
  • the hydrogen gas sensor 30 for altitude and the hydrogen gas sensor 20 for low concentration constitute a hydrogen gas sensor in the entire concentration range.
  • reference numeral 122 represents an air introduction pipe to the air pole 12
  • reference numeral 112 represents a hydrogen gas introduction pipe to the fuel pole 11.
  • the low-concentration hydrogen gas sensor 20 and the high-concentration hydrogen gas sensor 30 are in a low-concentration and high-concentration hydrogen gas environment, respectively, their installation locations are not limited to the above-mentioned locations.
  • the low-concentration gas sensor 20 shown in FIG. 1 includes a plate-shaped first electrode 21 and a second electrode 22 provided so as to face each other, and a solid electrolyte 23 is provided between these electrodes.
  • the structure is such that
  • the first electrode 21 functions as a detection electrode for hydrogen gas, and its electrostatic potential changes significantly when it comes into contact with hydrogen gas.
  • the second electrode 22 functions as a reference electrode for hydrogen gas, and its electrostatic potential hardly changes or even if it changes, it is extremely small when it comes into contact with hydrogen gas.
  • the first electrode 21 can be composed of a first electrode material having a relatively high chemical potential, specifically, a material having a relatively high adsorption activity to hydrogen gas such as platinum and a platinum alloy. be able to.
  • the first electrode 21 may be made of these materials themselves, but these materials can be supported on a predetermined substrate and used. However, it can be used in any embodiment as long as it does not deviate from the scope of the present invention and functions as a detection electrode for hydrogen gas.
  • the second electrode 22 can be made of a material having a relatively low chemical potential, and specifically, nickel, nickel alloy, titanium, titanium alloy, copper, copper alloy, iron, iron alloy, aluminum, aluminum alloy. It can also be composed of a material having a relatively low degree of adsorption activity for hydrogen gas, such as an organic conductive material. However, it can be used in any embodiment as long as it does not deviate from the scope of the present invention and functions as a reference electrode for hydrogen gas.
  • the first electrode 21 and the second electrode 22 have a plate shape, and the specific shape thereof can be various shapes such as linear, tubular, disc, and rectangular.
  • the solid electrolyte 23 can be composed of a solid electrolyte having excellent adhesion to the first electrode 21 and the second electrode 22, such as phosphotungstic acid.
  • the solid electrolyte 23 can include a structural reinforcing material such as glass wool in addition to an electrolyte material such as phosphotungsten. In this case, the strength of the solid electrolyte 23 can be increased, and the adhesion to the electrodes 21 and 22 can be further increased.
  • the high-concentration hydrogen gas sensor 30 basically takes the same mode as the hydrogen gas sensor shown in FIG. 2, but the third electrode 31 is required to have a hydrogen storage property. That is, in the case of a non-hydrogen storage electrode, for example, an electrode made of platinum or the like described above, when the hydrogen gas concentration at the electrode interface increases, the oxygen concentration at the electrode interface becomes relatively low. As a result, the change in EMF due to the reaction with oxygen becomes smaller, so that the change in EMF in the sensor is canceled out, and the change in EMF becomes smaller even if the hydrogen concentration increases.
  • a non-hydrogen storage electrode for example, an electrode made of platinum or the like described above
  • the hydrogen existing inside the electrode can keep the oxygen concentration at the electrode interface in a state where it can be substantially ignored. It can be sufficiently detected as a change.
  • Examples of the electrode material constituting the third electrode 31 include palladium and palladium alloys, Mg2Ni alloys, TiFeNiZi - based alloys, and the like, but palladium and palladium alloys having relatively high chemical potential are preferable.
  • the hydrogen gas sensor 20 having the first electrode 21 made of platinum or the like is suitable for detecting hydrogen gas under a low concentration
  • the hydrogen gas sensor 30 having the third electrode 31 made of palladium or the like has a high concentration. Suitable for detection of hydrogen gas sensor.
  • the fourth electrode 32 of the high-concentration hydrogen gas sensor 30 can be made of the same material as the second electrode 22 of the low-concentration hydrogen gas sensor 20, and can be used in the same manner.
  • the solid electrolyte 33 of the high-concentration hydrogen gas sensor 30 can also be made of the same material as the solid electrolyte 23 of the low-concentration hydrogen gas sensor, and can be used in the same manner.
  • the first electrode 21 and the second electrode 22 are provided with the first solid electrolyte 23 in contact with these electrodes, and the first electrode 21 is H 2 ( ⁇ )
  • a low concentration hydrogen gas concentration sensor containing a second electrode material exhibiting a value of less than 0.8 V, a third electrode 31 and a fourth electrode 32, and a second solid electrolyte 33 in contact with these electrodes are provided.
  • the third electrode 31 has a standard electromotive force value of 0.8 V or more in a cell composed of H 2 (-)
  • the fourth electrode 32 contains the third electrode material, and the fourth electrode 32 uses a hydrogen gas concentration sensor for high concentration containing the fourth electrode material showing a standard electromotive force value of less than 0.8 V in the cell having the same configuration. Therefore, the low concentration hydrogen gas sensor is responsible for detecting the hydrogen gas concentration under low concentration, and the high concentration hydrogen gas sensor is responsible for detecting the hydrogen gas concentration under high concentration. Therefore, hydrogen gas from low concentration to high concentration can be detected.
  • both the low-concentration hydrogen gas sensor 20 and the high-concentration hydrogen gas sensor 30 are configured such that the two electrodes constituting the hydrogen gas sensor contain materials having different chemical potentials with respect to hydrogen gas, and are relative to each other.
  • the first electrode 21 and the third electrode 31 containing a material having a relatively high chemical potential are used as detection electrodes, and the second electrode 22 and the fourth electrode 32 containing a material having a relatively low chemical potential are used as reference electrodes.
  • the hydrogen gas sensor 20 or 30 when the atmosphere contains hydrogen gas, the hydrogen gas sensor generates a predetermined electromotive force between electrodes containing materials having different chemical potentials. become. Therefore, even when the first electrode 21 and the second electrode 22 or the third electrode 31 and the fourth electrode 32 of the hydrogen gas sensor are in the same atmosphere, an electromotive force is generated between these electrodes and it is detected. This makes it possible to detect hydrogen gas in the atmosphere.
  • the hydrogen gas sensors 20 and 30 of the embodiment since the hydrogen gas concentration is detected based on the chemical potential, the hydrogen gas can be detected instantly.
  • the electromotive force between the two electrodes of the hydrogen gas sensors 20 and 30 of the embodiment is generated based on the following relational expression.
  • F is the Faraday constant
  • E is the EMF value
  • ⁇ I represents the electrostatic potential of the first electrode
  • ⁇ II represents the electrostatic potential of the second electrode.
  • the high and low hydrogen concentration means a low concentration when the concentration of hydrogen gas in the atmosphere is less than 10% by volume, and means a high concentration when the concentration of hydrogen gas in the atmosphere is 10% by volume or more.
  • At least one of the low-concentration hydrogen gas sensor 20 and the high-concentration hydrogen gas sensor 30 can be arranged on a strip-shaped insulating base material. Specifically, the film-shaped solid electrolytes 23 and 33 are formed, and the first electrode 21, the third electrode 31, the second electrode 22, and the fourth electrode 32 are provided on the film-like solid electrolytes 23 and 33 so as to be separated from each other.
  • the low-concentration hydrogen gas sensor 20 and the high-concentration hydrogen gas sensor 30 can be arranged in a limited space. This can be manufactured by incorporating it into a maintenance / replaceable piping screw or the like.
  • the hydrogen gas concentration sensors 20 and 30 shown in FIGS. 1 and 2 were placed in an atmosphere of an environmental temperature of 90 ° C. to ⁇ 50 ° C. and a humidity of 0% to 100% RH, and the hydrogen gas detection test was carried out.
  • the first electrode 21 of the low-concentration hydrogen gas sensor 20 was made of platinum
  • the third electrode 31 of the high-concentration hydrogen gas sensor 30 was made of palladium.
  • both the second electrode 22 and the fourth electrode 32 were made of tungsten.
  • Fuel cell 11 Fuel cell 12 Air electrode 13 Electrolyte 16 Case 20 Low concentration hydrogen gas sensor 21 1st electrode 22 2nd electrode 23 1st solid electrolyte 30 High concentration hydrogen gas sensor 31 3rd electrode 32 4th electrode 33 2nd solid Electrolytes

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
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  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Measuring Oxygen Concentration In Cells (AREA)
  • Fuel Cell (AREA)

Abstract

La présente invention comprend : un capteur de concentration de gaz hydrogène à faible concentration comprenant une première électrode, une deuxième électrode, et un premier électrolyte solide en contact avec les première et deuxième électrodes, la première électrode comprenant un premier matériau d'électrode présentant une valeur de force électromotrice standard dans une configuration de cellule prescrite d'au moins 0,8 V et la deuxième électrode comprenant un deuxième matériau d'électrode présentant une valeur de force électromotrice standard dans la même configuration de cellule inférieure à 0,8 V; et un capteur de concentration de gaz hydrogène à haute concentration comprenant une troisième électrode, une quatrième électrode, et un deuxième électrolyte solide en contact avec les troisième et quatrième électrodes, la troisième électrode comprenant un troisième matériau d'électrode à occlusion d'hydrogène présentant une valeur de force électromotrice standard dans une configuration de cellule prescrite d'au moins 0,8 V et la quatrième électrode comprenant un quatrième matériau d'électrode présentant une valeur de force électromotrice standard dans la même configuration de cellule inférieure à 0,8 V.
PCT/JP2020/046165 2020-10-15 2020-12-10 Capteur de concentration de gaz hydrogène de pile à combustible WO2022079925A1 (fr)

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JP2020174282A JP2022065582A (ja) 2020-10-15 2020-10-15 燃料電池用水素ガス濃度センサ
JP2020-174282 2020-10-15

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WO2022079925A1 true WO2022079925A1 (fr) 2022-04-21

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JP2024064282A (ja) * 2022-10-27 2024-05-14 株式会社新潟Tlo 水素ガス濃度センサ

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004519683A (ja) * 2001-04-06 2004-07-02 アドバンスド．テクノロジー．マテリアルス．インコーポレイテッド Ｈ２、ｎｈ３及び硫黄含有ガスを検知する微細加工薄膜センサーアレイ、並びにその製造及び使用方法
WO2005080957A1 (fr) * 2004-02-19 2005-09-01 Niigata Tlo Corporation Capteur de gaz hydrogène
JP2007017208A (ja) * 2005-07-06 2007-01-25 Hitachi Ltd ガス検知システム

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004519683A (ja) * 2001-04-06 2004-07-02 アドバンスド．テクノロジー．マテリアルス．インコーポレイテッド Ｈ２、ｎｈ３及び硫黄含有ガスを検知する微細加工薄膜センサーアレイ、並びにその製造及び使用方法
WO2005080957A1 (fr) * 2004-02-19 2005-09-01 Niigata Tlo Corporation Capteur de gaz hydrogène
JP2007017208A (ja) * 2005-07-06 2007-01-25 Hitachi Ltd ガス検知システム

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