WO2022259883A1 - Capteur de concentration de gaz hydrogène - Google Patents

Capteur de concentration de gaz hydrogène Download PDF

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Publication number
WO2022259883A1
WO2022259883A1 PCT/JP2022/021641 JP2022021641W WO2022259883A1 WO 2022259883 A1 WO2022259883 A1 WO 2022259883A1 JP 2022021641 W JP2022021641 W JP 2022021641W WO 2022259883 A1 WO2022259883 A1 WO 2022259883A1
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WIPO (PCT)
Prior art keywords
electrode
hydrogen gas
electrode piece
gas concentration
concentration sensor
Prior art date
Application number
PCT/JP2022/021641
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English (en)
Japanese (ja)
Inventor
修治 原田
和則 反町
克己 高木
洋司 結城
Original Assignee
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
Priority to JP2022558163A priority Critical patent/JPWO2022259883A1/ja
Publication of WO2022259883A1 publication Critical patent/WO2022259883A1/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
    • 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.
  • hydrogen concentration sensors for controlling hydrogen fuel cells in automobiles and heavy machinery efficiency use of hydrogen gas
  • hydrogen concentration sensors for liquids such as lubricating oil for generator bearings and transformer oil
  • hydrogen concentration sensor in medical chemicals such as kidney dialysis (promotes treatment effect by dissolving hydrogen)
  • hydrogen concentration sensor in solution such as hydrogen water, process control in chemical industry, etc.
  • the development of a hydrogen concentration sensor for gas is desired.
  • a hydrogen gas concentration sensor for shortening the detection time includes, for example, a first electrode and a second electrode made of materials having different chemical potentials with respect to hydrogen, and an electrolyte in contact with these electrodes.
  • a hydrogen gas sensor has been proposed that detects hydrogen gas based on the value of the electromotive force generated in (Patent Document 1).
  • the first electrode, the second electrode and the electrolyte are covered with an outer skin.
  • the first electrode, which is the sensing electrode be exposed from the skin and immersed in the liquid, while the electrolyte must be sealed from the liquid. Therefore, the structure of the hydrogen gas sensor becomes complicated, and the sealing method poses technical and economic problems.
  • An object of the present invention is to provide a hydrogen gas concentration sensor of a novel configuration capable of detecting the concentration of hydrogen gas present in environments such as special gases and liquids used in the chemical industry under high-temperature and high-humidity environments. aim.
  • the present invention is as described below.
  • the first electrode piece is a first electrode material exhibiting a standard electromotive force value of 0.8 V or more in a cell composed of H 2 ( ⁇ )
  • a hydrogen gas concentration sensor with a novel configuration that is capable of detecting the concentration of hydrogen gas in special gases and liquids used in the chemical industry under high-temperature and high-humidity environments.
  • FIG. 4 is a graph showing the EMF value when a platinum wire is used as the first electrode piece of the hydrogen gas concentration sensor in the example.
  • 4 is a graph showing EMF values when a palladium wire is used as the first electrode piece of the hydrogen gas concentration sensor in the example.
  • 4 is a graph showing the hydrogen gas concentration and the EMF value when a platinum wire is used as the first electrode piece of the hydrogen gas concentration sensor in the example.
  • 4 is a graph showing the relationship between the hydrogen gas concentration and the EMF value when a palladium wire is used as the first electrode piece of the hydrogen gas concentration sensor in the example.
  • FIG. 1 is a schematic configuration diagram of a hydrogen gas concentration sensor according to this embodiment.
  • the hydrogen gas concentration sensor 10 of this embodiment includes a first linear electrode piece 11, a second linear electrode piece 12, and an electrolyte 14 in which these electrode pieces are spaced apart. , and a container 15 with one end sealed to accommodate the first electrode piece 11 , the second electrode piece 12 and the electrolyte 14 .
  • the container 15 is arranged such that its tip is inserted into the system to be measured. Therefore, the inside of the container 15 is gas-insulated from the system to be measured.
  • the first electrode piece 11 functions as a hydrogen gas detection electrode, its tip penetrates through the sealed portion of the electrolyte 14 and is exposed to the outside of the container 15 .
  • the portion of the first electrode piece 11 that penetrates the container 15 is melt-sealed.
  • the second electrode piece 12 is made of a material with a relatively low chemical potential and does not affect the detection of hydrogen gas. Like the electrode piece 11 , it can be exposed to the outside from the sealed portion of the container 15 . However, in general, it is preferable not to expose the sensor 15 to the outside of the container 15 , because re-melting and sealing is generally required, which complicates the structure and manufacturing process of the hydrogen gas concentration sensor 10 .
  • the linear temperature compensating third electrode piece 13 is arranged to eliminate the influence of the environmental temperature. It is The third electrode piece 13 is also arranged with respect to the electrolyte 14 so as to be separated from the first electrode piece 11 and the second electrode piece 12 .
  • first electrode piece 11, the second electrode piece 12 and the third electrode piece 13 are connected to the rear end opening of the container 15 on the side opposite to the sealed portion of the container 15 in order to measure the electromotive force associated with the detection of the hydrogen gas concentration. It is arranged so as to extend outward from the container 15 from the part.
  • the first electrode piece 11 functions as a detection electrode for hydrogen gas, and when it comes into contact with hydrogen gas, the chemical potential of (atomic) hydrogen changes greatly.
  • the second electrode piece 12 functions as a reference electrode for hydrogen gas, and when it comes into contact with hydrogen gas, its chemical potential hardly changes or changes very little.
  • the first electrode piece 11 can be made of a first electrode material with a relatively high chemical potential, specifically H 2 ( ⁇ )
  • the above materials include materials with relatively high adsorption activity for hydrogen gas, such as platinum and platinum alloys.
  • the first electrode piece 11 can be composed of these materials themselves, these materials can be used by carrying them on a predetermined substrate. However, it can be used in any manner as long as it functions as a detection electrode for hydrogen gas without departing from the scope of the present invention.
  • the material described above it is also possible to use a material with relatively high adsorption activity for hydrogen gas, such as palladium or a palladium alloy.
  • the first electrode piece 11 can be made of these materials themselves, but these materials can also be used by carrying them on a predetermined substrate. However, it can be used in any manner as long as it functions as a detection electrode for hydrogen gas without departing from the scope of the present invention.
  • the hydrogen molecules are dissociated, so that the hydrogen gas adsorbed on the first electrode piece 11 is quickly detached. It is suitable as a detection electrode for a hydrogen gas concentration sensor that responds quickly, such as a hydrogen gas concentration sensor dissolved in water.
  • the first electrode piece 11 when the first electrode piece 11 is made of a palladium-based material, the amount of hydrogen corresponding to the hydrogen partial pressure dissolves in solid solution, but the dissolved hydrogen is difficult to escape. It takes time. Therefore, when the first electrode piece 11 is made of a palladium-based material, the first electrode piece 11 has a memory function and can be applied as a detection electrode suitable for checking deterioration of transformer oil, for example.
  • the second electrode piece 12 can be made of a material with a relatively low chemical potential, specifically H 2 ( ⁇ )
  • the second electrode material exhibits a cell standard electromotive force value of less than 0.8V.
  • the materials mentioned above include tungsten, tungsten alloys, nickel, nickel alloys, titanium, titanium alloys, copper, copper alloys, iron, iron alloys, aluminum, aluminum alloys and organic conductive materials, which have relatively high adsorption activity for hydrogen gas. Low degree materials can be mentioned. However, it can be used in any manner as long as it functions as a reference electrode for hydrogen gas without departing from the scope of the present invention.
  • the third electrode piece 13 is an electrode piece for temperature compensation, and is arranged to offset changes in the environmental temperature of the hydrogen gas concentration sensor 10, that is, the environmental temperature of the first electrode piece 11, which is the detection electrode. Therefore, it is preferable to use the same material as the first electrode piece 11 .
  • the electrolyte 14 can be composed of an electrolyte having excellent adhesion to the first electrode 21 and the second electrode 22, such as phosphotungstic acid. Electrolyte 14 may include structural reinforcements such as glass wool in addition to electrolyte materials such as phosphotungsten. In this case, the strength of the electrolyte 14 can be increased, and the adhesion between the first electrode piece 11 and the second electrode piece 12 can be further increased.
  • the container 15 is preferably made of glass, resin, ceramics, or the like in order to ensure insulation between the first electrode piece 11 and the second electrode piece 12 .
  • the container 15 is made of an electrically conductive material such as metal, it is preferable to insulate the first electrode piece 11 from the container 15 by coating it with resin or ceramic.
  • a first electrode material having a value of 0.8 V or more is included, and the second electrode piece 12 includes a second electrode material having a standard electromotive force value of less than 0.8 V in a cell with the same configuration.
  • the first electrode piece 11 penetrates the electrolyte 14 and has an end exposed outside from the container 15 .
  • the first electrode piece 11 exposed from the container 15 of the hydrogen gas concentration sensor 10 should be immersed in a liquid containing dissolved hydrogen gas. At this time, even if the tip portion of the container 15 is immersed in the liquid, the electrolyte 14 itself is housed and sealed in the container 15 and is therefore not immersed in the liquid. That is, the hydrogen gas concentration sensor 10 can detect the concentration of hydrogen gas dissolved in the liquid by means of the first electrode piece 11, which is the detection electrode, and the second electrode piece 12, which is the reference electrode, both of which are immersed in the liquid. can. Similarly, it is possible to detect the concentration of hydrogen gas in special gases such as those used in high-temperature, high-humidity environments or in the chemical industry.
  • the hydrogen gas concentration sensor 10 of this embodiment it is sufficient to immerse the tip portion in the liquid and immerse the first electrode piece 11 as the detection electrode in the liquid. Therefore, unlike the conventional sealed hydrogen gas concentration sensor, it is not necessary to expose at least the first electrode, which is the detection electrode, from the outer skin and immerse it in the liquid, and to seal the electrolyte from the liquid with the outer skin. That is, the hydrogen gas concentration can be detected with an extremely simple configuration.
  • the hydrogen concentration of the hydrogen gas concentration sensor 10 of this embodiment is detected by the electromotive force generated between the first electrode piece 11 and the second electrode piece 12.
  • the electromotive force is expressed by the following relational expression. generated based on
  • E is the EMF value
  • F Faraday constant
  • E the EMF value
  • ⁇ I the electrostatic potential of the first electrode
  • ⁇ II the electrostatic potential of the second electrode.
  • the temperature compensation by the third electrode piece 13 is ( ⁇ : adsorption energy, k: Boltzmann constant, T: temperature, n: hydrogen concentration) and can be done by subtracting this E value from the EMF value above.
  • the hydrogen concentration exceeds 1% (n is 0.01 or more)
  • the E value becomes a very small value, so temperature compensation does not need to be considered, and the third electrode piece 13 itself can also be omitted.
  • a hydrogen gas concentration sensor 10 shown in FIG. 1 was prepared, and a simple hydrogen gas detection test was carried out.
  • a platinum wire and a palladium wire with a diameter of 0.2 mm were used for the first electrode piece 11, and a tungsten wire with a diameter of 0.2 mm was used for the second electrode piece 12.
  • the third electrode piece 13 is omitted for simplification.
  • the first electrode piece 11 and the second electrode piece 12 are arranged on the electrolyte 14 made of cesium phosphotungstate with a gap of 0.2 mm.
  • 14 was housed in a glass tube 15 having a diameter of 6 mm and a length of 25 mm, and the first electrode piece 11 was exposed with a length of 3 mm from the tip of the glass tube 15 and melt-sealed. Note that the exposed portion may be cut off at the root portion.
  • the electrolyte and electrodes There are also no special restrictions on the arrangement of the electrolyte and electrodes.
  • the first electrode piece 11 and the second electrode piece 12 were exposed from the rear end side of the glass tube 15 so that the electromotive force could be measured by detecting the hydrogen gas concentration.
  • FIG. 2 shows the detected voltage (V) when a platinum wire is used as the first electrode piece 11
  • FIG. 3 shows the detected voltage (V) when a palladium wire is used as the first electrode piece 11.
  • the hydrogen gas concentration was adjusted by filling hydrogen gas into a sealed container having an opening for inserting the glass container 15, and the detected electromotive force was measured at the rear end opening of the glass tube 15. Measured at
  • the detection voltage decreases from 0.4 V to 0.03 V by detecting hydrogen gas. It can be seen that the electromotive force immediately recovers to 0.4 V when the voltage is cut off. That is, it can be seen that hydrogen gas desorbs quickly and is suitable as a detection electrode for a hydrogen gas concentration sensor with fast response. Assuming a fuel cell control sensor, the measurement result was obtained at a temperature of 85°C.
  • the hydrogen concentration was set to 10% to compare the responsiveness to hydrogen gas.
  • the value of the spontaneous electromotive force of the sensor which is a feature of the EMF type hydrogen sensor, was measured at the rear end opening of the glass tube 15 with an electrometer.
  • the hydrogen gas concentration sensor 10 configured as shown in FIG. 1 can detect the hydrogen gas concentration and functions as a sensor. Therefore, it can be seen that the hydrogen gas concentration sensor 10 shown in FIG. 1 can be applied to liquids such as oil to detect the concentration of hydrogen gas dissolved in these liquids.
  • the detection voltage increases as the hydrogen gas concentration increases while maintaining its memory function. That is, it can be seen that the hydrogen gas concentration sensor 10 configured as shown in FIG. 1 can detect the hydrogen gas concentration and functions as a sensor. Therefore, it can be seen that the hydrogen gas concentration sensor 10 shown in FIG. 1 can be applied to liquids such as oil to detect the concentration of hydrogen gas dissolved in these liquids.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Measuring Oxygen Concentration In Cells (AREA)

Abstract

La présente invention comprend une première partie d'électrode, une seconde partie d'électrode, un électrolyte dans lequel les parties d'électrode sont disposées à distance l'une de l'autre, et un récipient qui reçoit la première partie d'électrode, la seconde partie d'électrode, et l'électrolyte, la première partie d'électrode comprenant un premier matériau d'électrode présentant une valeur de force électromotrice standard d'au moins 0,8 V dans une cellule constituée de H2 (-), 50 mol/m3 de H2SO4, et un échantillon de substance (+) ; la seconde électrode comprend un second matériau d'électrode présentant une valeur de force électromotrice standard inférieure à 0,8 V dans une cellule ayant la même configuration ; et la première partie d'électrode pénètre à travers l'électrolyte et comporte une extrémité qui est exposée à l'extérieur du récipient.
PCT/JP2022/021641 2021-06-09 2022-05-26 Capteur de concentration de gaz hydrogène WO2022259883A1 (fr)

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JP2021096965 2021-06-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024090472A1 (fr) * 2022-10-27 2024-05-02 株式会社新潟Tlo Capteur de concentration d'hydrogène gazeux

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005080957A1 (fr) * 2004-02-19 2005-09-01 Niigata Tlo Corporation Capteur de gaz hydrogène
JP2007047124A (ja) * 2005-08-12 2007-02-22 Niigata Tlo:Kk 水素ガスセンサー
JP2008196903A (ja) * 2007-02-09 2008-08-28 Niigata Univ 水素量センサー
JP2009243962A (ja) * 2008-03-28 2009-10-22 Niigata Univ 水素ガスセンサ
JP2010230620A (ja) * 2009-03-30 2010-10-14 Niigata Univ 高濃度水素ガスセンサー
WO2011145150A1 (fr) * 2010-05-21 2011-11-24 国立大学法人新潟大学 Capteur d'hydrogène gazeux
JP2012163506A (ja) * 2011-02-09 2012-08-30 Gunze Ltd 油中水素検知センサ
JP2017044576A (ja) * 2015-08-26 2017-03-02 国立研究開発法人産業技術総合研究所 ガスセンサ及びガスの検知方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005080957A1 (fr) * 2004-02-19 2005-09-01 Niigata Tlo Corporation Capteur de gaz hydrogène
JP2007047124A (ja) * 2005-08-12 2007-02-22 Niigata Tlo:Kk 水素ガスセンサー
JP2008196903A (ja) * 2007-02-09 2008-08-28 Niigata Univ 水素量センサー
JP2009243962A (ja) * 2008-03-28 2009-10-22 Niigata Univ 水素ガスセンサ
JP2010230620A (ja) * 2009-03-30 2010-10-14 Niigata Univ 高濃度水素ガスセンサー
WO2011145150A1 (fr) * 2010-05-21 2011-11-24 国立大学法人新潟大学 Capteur d'hydrogène gazeux
JP2012163506A (ja) * 2011-02-09 2012-08-30 Gunze Ltd 油中水素検知センサ
JP2017044576A (ja) * 2015-08-26 2017-03-02 国立研究開発法人産業技術総合研究所 ガスセンサ及びガスの検知方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024090472A1 (fr) * 2022-10-27 2024-05-02 株式会社新潟Tlo Capteur de concentration d'hydrogène gazeux

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