US20050252789A1 - Hydrogen sensing apparatus and method - Google Patents

Hydrogen sensing apparatus and method Download PDF

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Publication number
US20050252789A1
US20050252789A1 US10/527,347 US52734705A US2005252789A1 US 20050252789 A1 US20050252789 A1 US 20050252789A1 US 52734705 A US52734705 A US 52734705A US 2005252789 A1 US2005252789 A1 US 2005252789A1
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hydrogen
metal
solid electrolyte
reference standard
electrolyte
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Derek Fray
Carsten Schwandt
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Cambridge Enterprise Ltd
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Assigned to CAMBRIDGE UNIVERSITY reassignment CAMBRIDGE UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FRAY, DEREK JOHN, SCHWANDT, CARSTEN
Publication of US20050252789A1 publication Critical patent/US20050252789A1/en
Assigned to FOSECO INTERNATIONAL LIMITED reassignment FOSECO INTERNATIONAL LIMITED DISTRIBUTION AGREEMENT Assignors: ENVIRONMENTAL MONITORING & CONTROL LIMITED
Assigned to FOSECO INTERNATIONAL LIMITED reassignment FOSECO INTERNATIONAL LIMITED PATENT AND KNOW-HOW LICENSE AGREEMENT Assignors: CAMBRIDGE UNIVERSITY TECHNICAL SERVICES LIMITED, ENVIRONMENTAL MONITORING AND CONTROL LIMITED
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Priority to US13/187,207 priority Critical patent/US9028671B2/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/005—H2
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen

Definitions

  • the present invention relates to apparatus and a method for measuring the concentration of hydrogen in fluid media at elevated temperatures using a high temperature proton-conducting solid electrolyte in conjunction with an internal hydrogen standard.
  • One concept of constructing hydrogen sensors for operation at elevated temperatures is to utilise a proton conducting solid electrolyte that compares the hydrogen partial pressure on the measuring side with a known and fixed hydrogen partial pressure on the reference side.
  • the most appropriate proton conducting solid electrolytes are perovskites, with doped strontium cerate (SrCe 0.95 Yb 0.05 O 3-d ) and doped calcium zirconate (CaZr 0.9 In 0.1 O 3-d ) being applied most frequently. Under the relevant experimental conditions, these materials exhibit predominant proton conductance.
  • Electrodes are formed by covering the surface of the electrolyte with a catalytically active and electronically conducting material, for instance platinum. If two electrodes on different areas of the same electrolyte body are brought into contact with two media of different hydrogen contents, i.e., p′H2 and p′′H2, a hydrogen concentration cell is formed:
  • U the electromotive force (emf)
  • R the universal gas constant
  • T the absolute temperature
  • F Faraday's constant
  • p′′H2 and p′H2 are the hydrogen partial pressures at the measuring electrode and the reference electrode, respectively:
  • U - RT 2 ⁇ F ⁇ ln ⁇ ⁇ p H 2 ′′ p H 2 ′ .
  • the invention provides apparatus and methods for sensing hydrogen concentration as defined in the appended independent claims. Preferred or advantageous features of the invention are set out in dependent subclaims.
  • the present invention may thus provide an apparatus for measuring hydrogen concentration, comprising a proton-conducting solid electrolyte in conjunction with a self-contained and hermetically sealed metal/hydrogen reference standard, of which the content and/or the spatial distribution of oxygen is appropriate substantially to prevent chemical reaction between the solid electrolyte and the reference material, particularly at the interface there between.
  • the present invention may thus advantageously provide a sensor with a novel hydrogen standard that establishes a defined and reproducible reference hydrogen partial pressure and ensures chemical stability of the electrolyte/reference interface.
  • a metal/hydrogen two-phase/two-component mixture (being a solution of hydrogen in the metal such that, under the conditions of use of the apparatus, the solution lies within a two-phase field of the metal-hydrogen phase diagram) may be used as an internal hydrogen standard in sensors employing an oxide-based proton-conducting solid electrolyte, because this type of mixture is able to fix the hydrogen partial pressure inside an encapsulated volume adjacent to the electrolyte and, second, may advantageously enable the interface between the electrolyte and the reference to be chemically stable.
  • the second issue may be fulfilled by maintaining a suitable oxygen activity in the reference material, which is both sufficiently high in order to guarantee chemical stability in contact with the oxide-based electrolyte, so the proton conducting properties of the latter are not affected, and sufficiently low in order pot to invalidate the two-phase/two-component approach.
  • a suitable oxygen activity in the reference material which is both sufficiently high in order to guarantee chemical stability in contact with the oxide-based electrolyte, so the proton conducting properties of the latter are not affected, and sufficiently low in order pot to invalidate the two-phase/two-component approach.
  • the appropriate oxygen concentration, or range of oxygen concentration, required to achieve this in any particular case may depend not only on the oxygen activity required for proper operation of the reference standard but also on the chemical stability of the electrolyte material.
  • the proton conducting solid electrolyte is a perovskite, preferably SrCe 0.95 Yb 0.05 O 3- ⁇ or CaZr 0.9 In 0.1 O 3- ⁇
  • the metal component of the metal/hydrogen reference system is titanium, zirconium or hafnium.
  • the metal in the reference standard may be an alloy and the reference standard may contain other elements which affect its phase diagram. Nevertheless, the quantitative predominance of the respective metal and hydrogen in the two-phase mixture guarantee that the chemical potential and the activity of the two components, i.e., the respective metal and hydrogen, are thermodynamically fixed in terms of Gibbs' phase rule. This means that, within the range of the two-phase area (within which the two phases of the metal can coexist), the hydrogen activity is independent of the composition of the reference system and also does not change when the composition undergoes small variations during sensor operation.
  • the hydrogen activity of the reference system may be determined from literature data and is only a function of temperature. Knowledge of the reference hydrogen partial pressure for the given temperature permits direct determination of the hydrogen partial pressure on the measuring side.
  • the ⁇ -titanium/ ⁇ -titanium two-phase region is preferred whilst the ⁇ -titanium/ ⁇ -titanium two-phase region is less suitable because the corresponding hydrogen partial pressures are beyond atmospheric pressure.
  • zirconium both the ⁇ -zirconium/ ⁇ -zirconium and the ⁇ -zirconium/ ⁇ -zirconium two-phase areas may be used, but the latter is preferred because of its extended composition range at elevated temperatures.
  • Concerning hafnium only the ⁇ -hafnium/ ⁇ -hafnium two-phase region is appropriate.
  • a chemically stable interface between the solid electrolyte and the reference material may advantageously be ensured. It is important to note that even minute changes in the oxygen concentration may have a dramatic impact on the electrochemical properties of oxide-based proton conducting solid electrolytes. In fact, the release of small amounts of oxygen has been shown to convert these materials from pure proton conductors into mixed conductors, oxygen ion conductors or semiconductors, which makes them inappropriate for the application envisaged. Accordingly, very reactive metals like alkali metals, alkaline earth metals and rare earth metals, which also form two-phase areas with hydrogen, are not preferred for use as the reference material, since they reduce the oxide-based solid electrolyte at elevated temperatures.
  • the signal of a sensor which is constructed in accordance with the above requirements, may advantageously be used to determine directly the hydrogen content in a fluid medium. If the composition of the medium needs to be controlled, the composition may then be varied until the required signal is recorded.
  • FIG. 1 is a schematic illustration of an apparatus according to an embodiment of the invention
  • FIG. 2 is a plot of the measured cell potential when using sensors with the ⁇ -titanium/ ⁇ -titanium+hydrogen (+oxygen) reference system to measure hydrogen concentration in hydrogen/argon gas mixtures of known hydrogen concentration at different temperatures;
  • FIG. 3 is a plot of the measured cell potential when using sensors with the ⁇ -zirconium/ ⁇ -zirconium+hydrogen (+oxygen) reference system to measure hydrogen concentration in hydrogen/argon gas mixtures of known hydrogen concentration at different temperatures;
  • FIG. 4 is a plot of the measured cell potential when using sensors with the ⁇ -hafnium/ ⁇ -hafnium+hydrogen (+oxygen) reference system to measure hydrogen concentration in hydrogen/argon gas mixtures of known hydrogen concentration at different temperatures;
  • FIG. 5 is a schematic illustration of an apparatus according to a second embodiment of the invention.
  • FIG. 1 shows a schematic illustration of a preferred embodiment of the invention, comprising a solid electrolyte body 1 , a reference material 2 , an inert packing material 5 , a glass seal 6 , a catalytic coating at a reference electrode 3 , a catalytic coating at a measuring electrode 4 , a lead to the reference electrode 7 , a lead to the measuring electrode 8 , and an electronic measuring unit 9 .
  • the solid electrolyte is shaped as a tube, closed at one end, with a length of about 20 mm and a diameter of about 5 mm, but it may be appreciated that the precise dimensions are not critical. This solid electrolyte shape may be described as a thimble.
  • the electrolyte material is a perovskite.
  • a catalytic coating may be applied to the interior and the exterior surfaces of the electrolyte tube. Electrical leads may be placed on both surfaces. In the preferred embodiment, the catalytic coatings and the electrical leads are made from platinum.
  • the reference material is titanium/hydrogen, zirconium/hydrogen or hafnium/hydrogen and is placed inside the electrolyte tube.
  • the reference material is encapsulated by means of a suitable sealing material.
  • a suitable sealing material When applying an oxide-based sealing glass, the silicon content must be low in order to prevent detrimental reactions between the hydrogen in the reference compartment and the silicon in the glass, which would result in decomposition of the reference material.
  • a silicon-free glass based on the oxides of aluminium, barium, boron, calcium and magnesium is used. The direct contact of the reference material and the sealing material may be detrimental.
  • an inert packing material like pure calcium zirconate or yttrium oxide serves as a separator between both these components.
  • FIG. 5 An example is shown in FIG. 5 , in which an electrolyte layer 20 is placed beneath a reference standard layer 22 , both formed as disc-shaped pellets.
  • a packing material 24 covers the upper and side surfaces of the reference standard layer and the stack thus formed is sealed in a glass casing 26 , leaving only one face of the electrolyte exposed for access to media in which hydrogen concentration is to be measured.
  • the packing material separates the reference standard layer from the sealing glass to prevent chemical degradation. Electrical connections to the probe are formed by layers applied to the upper and lower electrolyte surfaces, in the same way as described in other embodiments.
  • the first procedure consists of two steps.
  • a quantity of titanium, zirconium or hafnium metal is inserted into the open end of the solid electrolyte tube, or thimble, and a seal across the open end of the tube is created by melting and then solidifying a solder glass under an atmosphere of an inert gas or hydrogen gas or a mixture thereof.
  • the residual oxygen content should be low in order to avoid oxidation of the metal.
  • the seal ensures that the metal is in contact with the electrolyte but hermetically sealed from the environment.
  • an electric current is applied such that hydrogen is electrochemically transported into or out of the reference compartment until the metal to hydrogen atomic ratio is suitable for the metal/hydrogen mixture to function as a reference standard for hydrogen.
  • This method of preparation is preferred for the use of titanium/hydrogen as the reference system.
  • the second procedure consists of only one step.
  • a quantity of titanium, zirconium or hafnium metal is inserted into the open end of the solid electrolyte tube, or thimble, and a seal is created by melting and solidifying a solder glass under a hydrogen-containing atmosphere while, simultaneously, the reference is being formed through hydrogen uptake by the metal from the gas.
  • the metal/hydrogen mixture it is important to match the melting temperature of the glass and the hydrogen content of the gas atmosphere such that, after formation of the seal, the metal to hydrogen atomic ratio in the metal/hydrogen reference is inside the desired two-phase area.
  • This method of preparation is preferred for the use of zirconium/hydrogen or hafnium/hydrogen as the reference system.
  • preconditioning is carried out at elevated temperature, preferentially beyond 700° C., in a humidified gas atmosphere of low hydrogen partial pressure, preferentially below 1% by volume.
  • the apparatus may be placed directly into the medium to be analysed, which may be stagnant or flowing, at a temperature sufficient for the solid electrolyte to conduct ionically.
  • a temperature is in the range of 500° C. to 900° C.
  • the sensors were found to detect hydrogen contents from at least 100 ppm to 100% by volume.
  • High density ceramic thimbles of indium oxide doped calcium zirconate (CaZr 0.9 In 0.1 O 3-d ) were obtained through isostatic pressing of a suitable powder and sintering at 1600° C. in air for 8 h. Porous platinum electrodes were generated by firing a platinum-containing ink at 1000° C. in air for 1 h. Platinum lead wires were attached to both platinum coatings.
  • the hydrogen Prior to application, the hydrogen was passed through calcium sulphate to remove traces of moisture and through a suitable metal scrubber to ensure low residual oxygen content. The unit was then exposed to a 1% by volume hydrogen in argon gas mixture at 700° C. and coulometric titration was performed. To that end, a direct current of around 60 mA, this typically corresponding to voltages in the range of a few hundred millivolts, was applied for about 200 h, with the inner electrode connected to the positive terminal and the outer electrode connected to the negative terminal. By way of this procedure, a quantity of hydrogen was removed from the reference compartment, such that the titanium to hydrogen ratio established in the reference system was inside the ⁇ -titanium/ ⁇ -titanium two-phase area.
  • the senor was preconditioned at 800° C. in argon, which had been humidified by passing through a water bubbler at room temperature, for at least 1 h.
  • Sensor measurements were performed between 500 and 800° C. in hydrogen/argon mixtures with hydrogen contents of 10 ppm, 100 ppm, 1%, 10% and 100% by volume. Measured emfs are shown in FIG. 2 .
  • the data are in good agreement with thermodynamically expected values.
  • Sensor signals were stable, with a drift of typically less than 1 mV/d, and the response time to changes in temperature and hydrogen partial pressure was in the order of minutes. Variations in the results for different sensors were found to be less than 5%.
  • indium oxide doped calcium zirconate electrolyte was reduced by grade 1 or grade 2 titanium but not by grade 4 titanium suggests an acceptable range of oxygen concentration for this combination of materials.
  • different electrolyte materials used with titanium-based reference standards may require different oxygen concentrations in the titanium.
  • a more stable electrolyte may tolerate lower oxygen concentrations in the titanium.
  • zirconium metal About 100 mg of zirconium metal were cut from a commercial zirconium wire with a known bulk oxygen content of 1500 ppm by mass and placed inside a ceramic calcium zirconate thimble.
  • the interior of the thimble was filled with yttrium oxide powder, which acts as an inert packing material, and this was covered with a layer of silicon-free sealing glass powder as described in example 1.
  • yttrium oxide powder acts as an inert packing material
  • silicon-free sealing glass powder as described in example 1.
  • the arrangement was heated to around 940° C. in an alumina tube under pure hydrogen.
  • a zirconium to hydrogen ratio inside the ⁇ -zirconium/ ⁇ -zirconium two-phase area was established directly. Preconditioning of the sensor was carried out as described in example 1. Sensor measurements were performed between 500° C.
  • the above zirconium material could be employed successfully both in the as-received and in the grit-blasted state.
  • a different zirconium wire with a bulk oxygen content of 1010 ppm by mass, was found to work successfully only in the as-received state, then providing similar results to the ones shown in FIG. 3 .
  • no stable signals were achieved. This suggests that the particular material possesses an oxygen-rich surface layer which renders the electrolyte/reference interface stable if used in the as-received state, but that the bulk oxygen content is too low to allow for a stable interface once the outer layer is removed.
  • hafnium metal About 200 mg of hafnium metal were cut from a commercial hafnium wire with a known oxygen content of 230 ppm by mass and placed inside a ceramic calcium zirconate thimble. 1.0 mg of titanium dioxide was added. The interior of the thimble was filled with yttrium oxide powder, which acts as an inert packing material, and this was covered with a layer of a laboratory-made silicon-free sealing glass powder, which has a melting point of approximately 970° C. To melt the glass and form the seal, the arrangement was heated to around 980° C. in an alumina tube under pure hydrogen. By way of this procedure, a hafnium to hydrogen ratio inside the ⁇ -hafnium/ ⁇ -hafnium two-phase area was established directly.
  • Preconditioning of the sensor was carried out as described in example 1. Sensor measurements were performed between 600 and 800° C. in hydrogen/argon mixtures with hydrogen contents of 1, 10 and 100% by volume. Measured emfs are shown in FIG. 4 . Sensor performance was again found to be good.
  • the above hafnium wire could be used neither in the as-received nor in the grit-blasted state.
  • the bulk oxygen content is too low to allow for a stable electrolyte/reference interface and, secondly, that the oxygen-rich surface layer, if any, is too thin to prevent oxygen uptake of the reference material from the electrolyte. So, it is only through the formation of a passivating surface layer, brought about by the decomposition of titanium dioxide in the presence of hydrogen gas and subsequent precipitation of oxygen-containing species on the hafnium wire, that stability of the electrolyte/reference interface is provided.

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Cited By (8)

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WO2009015662A1 (de) * 2007-07-30 2009-02-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur bestimmung von diffusions- und/oder austauschkoeffizienten eines mischleitenden werkstoffs
US20090127133A1 (en) * 2004-10-01 2009-05-21 Environmental Monitoring And Control Limited Apparatus and Method for Measuring Hydrogen Concentration in Molten Metals
US20090139876A1 (en) * 2005-10-12 2009-06-04 Enviromental Monitoring And Control Limited Apparatus and Method for Measuring Hydrogen Concentration
US20100194534A1 (en) * 2007-07-24 2010-08-05 Vinko Kunc Radio frequency identification system provided for access control
CN105319253A (zh) * 2015-11-12 2016-02-10 东北大学 一种测量金属熔体中氢含量的传感器及测量方法
KR20160122466A (ko) * 2015-04-14 2016-10-24 한국과학기술원 수소 가스센서
JP2018179830A (ja) * 2017-04-17 2018-11-15 株式会社みらくるセンター 水中の水素溶存量測定方法
CN114072665A (zh) * 2019-07-01 2022-02-18 东京窑业株式会社 固体参比物质和氢气传感器

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GB0822734D0 (en) 2008-12-12 2009-01-21 Environmental Monitoring And C Method and apparatus for monitoring gas concentration
KR101325508B1 (ko) 2012-03-14 2013-11-07 한국과학기술원 고체 산소이온 전도체와 고체 수소이온 전도체의 접합구조를 가진 용융금속 내 수소 측정 센서
US20150330938A1 (en) 2012-12-07 2015-11-19 Environmental Monitoring And Control Limited Method and apparatus for monitoring gas concentration
JP6165343B2 (ja) * 2013-09-12 2017-07-19 コリア・アドバンスト・インスティテュート・オブ・サイエンス・アンド・テクノロジー 液体内の溶存水素ガス濃度測定用水素センサ素子およびこれを用いた水素ガス濃度測定方法
RU2602757C2 (ru) * 2014-12-15 2016-11-20 Открытое Акционерное Общество "Акмэ-Инжиниринг" Датчик водорода в газовых средах

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Cited By (13)

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Publication number Priority date Publication date Assignee Title
US20090127133A1 (en) * 2004-10-01 2009-05-21 Environmental Monitoring And Control Limited Apparatus and Method for Measuring Hydrogen Concentration in Molten Metals
US8152978B2 (en) * 2004-10-01 2012-04-10 Environmental Monitoring And Control Limited Apparatus and method for measuring hydrogen concentration in molten metals
US20090139876A1 (en) * 2005-10-12 2009-06-04 Enviromental Monitoring And Control Limited Apparatus and Method for Measuring Hydrogen Concentration
US20100194534A1 (en) * 2007-07-24 2010-08-05 Vinko Kunc Radio frequency identification system provided for access control
US8368411B2 (en) 2007-07-30 2013-02-05 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V Method for determining diffusion and/or transfer coefficients of a material
WO2009015662A1 (de) * 2007-07-30 2009-02-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur bestimmung von diffusions- und/oder austauschkoeffizienten eines mischleitenden werkstoffs
KR102315252B1 (ko) 2015-04-14 2021-10-21 한국과학기술원 수소 가스센서
KR20160122466A (ko) * 2015-04-14 2016-10-24 한국과학기술원 수소 가스센서
CN105319253A (zh) * 2015-11-12 2016-02-10 东北大学 一种测量金属熔体中氢含量的传感器及测量方法
US10598629B2 (en) 2015-11-12 2020-03-24 Northeastern University Sensor and measurement method for measuring hydrogen content in metal melt
WO2017080005A1 (zh) * 2015-11-12 2017-05-18 东北大学 一种测量金属熔体中氢含量的传感器及测量方法
JP2018179830A (ja) * 2017-04-17 2018-11-15 株式会社みらくるセンター 水中の水素溶存量測定方法
CN114072665A (zh) * 2019-07-01 2022-02-18 东京窑业株式会社 固体参比物质和氢气传感器

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US9028671B2 (en) 2015-05-12
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