WO2008062561A1 - Dispositif de mesure, pile à combustible comportant un tel dispositif, et procédé de mesure - Google Patents

Dispositif de mesure, pile à combustible comportant un tel dispositif, et procédé de mesure Download PDF

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Publication number
WO2008062561A1
WO2008062561A1 PCT/JP2007/001283 JP2007001283W WO2008062561A1 WO 2008062561 A1 WO2008062561 A1 WO 2008062561A1 JP 2007001283 W JP2007001283 W JP 2007001283W WO 2008062561 A1 WO2008062561 A1 WO 2008062561A1
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WO
WIPO (PCT)
Prior art keywords
coil
permanent magnet
magnetic field
film
region
Prior art date
Application number
PCT/JP2007/001283
Other languages
English (en)
Japanese (ja)
Inventor
Kuniyasu Ogawa
Tomoyuki Haishi
Kohei Ito
Original Assignee
Keio University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006315563A external-priority patent/JP5046203B6/ja
Application filed by Keio University filed Critical Keio University
Publication of WO2008062561A1 publication Critical patent/WO2008062561A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
    • G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
    • G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
    • G01N24/082—Measurement of solid, liquid or gas content
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/28—Details of apparatus provided for in groups G01R33/44 - G01R33/64
    • G01R33/38—Systems for generation, homogenisation or stabilisation of the main or gradient magnetic field
    • G01R33/3808—Magnet assemblies for single-sided MR wherein the magnet assembly is located on one side of a subject only; Magnet assemblies for inside-out MR, e.g. for MR in a borehole or in a blood vessel, or magnet assemblies for fringe-field MR
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/28—Details of apparatus provided for in groups G01R33/44 - G01R33/64
    • G01R33/38—Systems for generation, homogenisation or stabilisation of the main or gradient magnetic field
    • G01R33/383—Systems for generation, homogenisation or stabilisation of the main or gradient magnetic field using permanent magnets
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
    • G01R33/48—NMR imaging systems
    • G01R33/54—Signal processing systems, e.g. using pulse sequences ; Generation or control of pulse sequences; Operator console
    • G01R33/56—Image enhancement or correction, e.g. subtraction or averaging techniques, e.g. improvement of signal-to-noise ratio and resolution
    • G01R33/561—Image enhancement or correction, e.g. subtraction or averaging techniques, e.g. improvement of signal-to-noise ratio and resolution by reduction of the scanning time, i.e. fast acquiring systems, e.g. using echo-planar pulse sequences
    • G01R33/5615—Echo train techniques involving acquiring plural, differently encoded, echo signals after one RF excitation, e.g. using gradient refocusing in echo planar imaging [EPI], RF refocusing in rapid acquisition with relaxation enhancement [RARE] or using both RF and gradient refocusing in gradient and spin echo imaging [GRASE]
    • G01R33/5617—Echo train techniques involving acquiring plural, differently encoded, echo signals after one RF excitation, e.g. using gradient refocusing in echo planar imaging [EPI], RF refocusing in rapid acquisition with relaxation enhancement [RARE] or using both RF and gradient refocusing in gradient and spin echo imaging [GRASE] using RF refocusing, e.g. RARE
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04492—Humidity; Ambient humidity; Water content
    • H01M8/04529—Humidity; Ambient humidity; Water content of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/28—Details of apparatus provided for in groups G01R33/44 - G01R33/64
    • G01R33/32—Excitation or detection systems, e.g. using radio frequency signals
    • G01R33/34—Constructional details, e.g. resonators, specially adapted to MR
    • G01R33/341—Constructional details, e.g. resonators, specially adapted to MR comprising surface coils
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
    • G01R33/48—NMR imaging systems
    • G01R33/50—NMR imaging systems based on the determination of relaxation times, e.g. T1 measurement by IR sequences; T2 measurement by multiple-echo sequences
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • Measuring device fuel cell including the same, and measuring method
  • the present invention relates to a measuring apparatus, a fuel cell including the same, and a measuring method, and more particularly, to a background art relating to a technique for locally measuring the distribution of the amount of a protic solvent in a membrane
  • a functional material such as a membrane
  • the amount of solvent in the material may dominate the performance of the material.
  • functional materials include solid polymer electrolyte membranes used in fuel cells.
  • a gas containing water vapor is supplied as a fuel and an oxidant from a flow channel formed in a separator during operation.
  • the supply of fuel and oxidant causes a distribution in the amount of water in the solid polymer electrolyte membrane, and the distribution state changes with time.
  • Patent Document 1 As a technique for locally measuring the amount of the protonic solvent at a specific portion of a sample, there is a conventional one described in Patent Document 1.
  • the Malczech method is applied locally to a specific part of the sample, the relaxation time constant is measured by 1 H-NMR, and the amount of the protonic solvent in the specific part of the sample is measured locally.
  • the technology to do is described. According to this technique, it is possible to measure the amount of local protonic solvent at a specific location in a substance in a relatively short time using the measurement result of NMR.
  • Patent Document 2 As another conventional technique related to NMR measurement of a sample, Patent Document 2 and And those described in 3.
  • Patent Document 2 describes that NMR measurement of a sample is performed using a U-shaped magnet and a solenoid coil.
  • Patent Document 3 describes a moisture distribution measuring device for a polymer film. In this method, the MR I image of the polymer membrane is acquired and the moisture distribution is acquired.
  • Patent Document 1 International Publication No. 2006/030743 Pamphlet
  • Patent Document 2 Japanese Patent Application Laid-Open No. 54-1 27785
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004_1070297
  • Non-special text ⁇ Tsushima Si ⁇ n 2 3 ⁇ 4 “Magnetic resonance imaging of the wa ter distribution within a polymer electrolyte membrane in fuel eel Is J, ELECTROCHEMICAL AND SOLID-STATE LETTERS, 7 (9), A269-A272, 2004
  • Non-Patent Document 2 Keigo Takenaka, “Solid Polymer Electrolyte Water Electrolysis Technology and Its Applications”, Soda and Chlorine, Vo, 37, p. 323-337 (1 986)
  • the characteristics of the film can be measured.
  • the above-described solid polymer electrolyte membrane of a fuel cell is useful for optimal control of the operating state during battery operation.
  • a device for measuring the spatial distribution of the amount of the protonic solvent in the membrane is required.
  • the conventional measuring device described above has a protonic solvent from a specific part of the membrane. It was not always suitable for measuring the amount of protonic solvent in the membrane as it diffused into the membrane.
  • a solvent amount calculation unit that calculates the amount of the protonic solvent at a specific location of the membrane
  • the permanent magnet is provided with a channel groove through which a fluid containing the protonic solvent flows.
  • a measuring device is provided in which the film is provided in parallel to the flow path forming surface of the permanent magnet.
  • a film is arranged in parallel to the flow path forming surface of the permanent magnet formed with the flow path groove, and the amount of the protonic solvent at a specific location in the film is locally measured using a nuclear magnetic resonance method.
  • a measurement method is provided.
  • a static magnetic field is applied to the film, and a proton solvent is flowed into the flow path groove so that the protons in the film.
  • a distribution can be formed in the amount of the organic solvent. Then, by applying an excitation oscillating magnetic field to the part of the film on which the distribution of the amount of the protonic solvent is formed using an RF coil, an echo signal is obtained, thereby distributing the protonic solvent in the film. Can be detected.
  • the film is arranged in parallel to the flow path forming surface of the permanent magnet, it is possible to reliably align the measurement location when performing the measurement using the permanent magnet having a specific shape and the RF coil.
  • the amount of protonic solvent in the membrane can be measured in situ.
  • the membrane can have a desired It can adjust so that it may become a tonality solvent amount.
  • an RF coil is used to excite part of the membrane.
  • the measuring apparatus of the present invention can be incorporated into a fuel cell, for example.
  • an echo signal can be obtained by performing measurement while flowing a fluid containing a protonic solvent in the flow channel groove of the permanent magnet. It is not essential in the present invention to flow the fluid in the flow channel, and the measurement may be performed in a state in which no fluid flows.
  • the protonic solvent include water and alcohols such as methanol and ethanol.
  • the “echo signal” may be a signal that corresponds to the excitation oscillating magnetic field and functions as an NMR signal capable of calculating the T 2 relaxation time constant.
  • static magnetic field is completely a magnetic field that is stable in time to such an extent that the echo signal and the T 2 relaxation time constant can be acquired stably. It does not have to be a stable magnetic field, and there may be some variation within that range.
  • the solvent amount calculating section from the intensity of the echo signal, and calculates the T 2 relaxation time constant, from the calculated said T 2 relaxation time constant, specific portions of the film
  • the amount of the protonic solvent in may be calculated.
  • the second step is from the strong degree of the echo signals, calculating a T 2 relaxation time constant, the pro tons of solvent content and T 2 relaxation time constant in the film acquires data indicating the correlation, including from the said data and T 2 wherein T 2 relaxation time constant calculated in the step of calculating the relaxation time constant, and determining the amount of the pro ton solvent, the You may go out.
  • the magnitude of the static magnetic field changes along the normal direction of the surface.
  • a spatial distribution different from the case where there is no flow path occurs in the magnitude of the static magnetic field in the upper part of the flow path forming surface.
  • the resonance frequency in the measurement of the membrane changes depending on the strength of the static magnetic field at the measurement location, so that the echo signal can be acquired reliably.
  • the flow path groove of the permanent magnet may include a plurality of groove portions arranged in parallel to each other.
  • the projections (flow channel forming surface) formed between the plurality of groove portions are separated from the flow channel forming surface at a specific interval. Can be supported. Therefore, the distance between the film and the flow path forming surface in the ray direction of the flow path forming surface can be maintained in a state of being regulated to a specific size, and the film can be stably held in the vicinity of the flow path forming surface.
  • one surface of the film may be in direct contact with the flow path forming surface of the permanent magnet, or the distance adjustment made of a nonmagnetic material between the flow path forming surface and the film.
  • a member may be interposed.
  • the RF coil may form the excitation oscillating magnetic field having an amplitude in a direction in the flow path forming plane and perpendicular to the extending direction of the groove. .
  • the magnetostatic field intensity in the plane parallel to the flow path formation surface is uniform in the following areas (i) and (ii) in the upper area of the flow path formation surface. Regions can be formed.
  • the region (i) is formed by extending the groove portion in a plane parallel to the flow path forming surface. This is a region where the change in the direction of the static magnetic field is small.
  • the region (ii) is defined by the extending direction of the groove in the plane parallel to the flow path forming surface. This is the region where the change of the static magnetic field is small.
  • the RF coil includes a pair of coil portions, and the excitation is performed in a region sandwiched between the pair of coil portions.
  • the RF coil is a plane in which the first coil portion including the first linear region and the second coil portion including the second linear region are connected.
  • the first coil portion and the second coil portion are conductive coils, and the first linear region and the second linear region are parallel to the extending direction of the groove portion.
  • the region sandwiched between the first straight region and the second straight region when viewed from above the flow path forming surface of the permanent magnet is located within the region sandwiched between the adjacent groove portions. It may be a configuration included in
  • the linear region of the RF coil By arranging the linear region of the RF coil on the upper part of the flow path forming surface of the permanent magnet, the region where the static magnetic field strength is uniform in the plane parallel to the flow channel groove forming surface is defined as the measurement region. can do.
  • the straight region can be directly or indirectly supported by the flow path forming surface by arranging the straight region above the flow path forming surface, the gap between the flow path forming surface and the straight region can be reduced. This further suppresses the measurement of the amount of protonic solvent with higher accuracy.
  • the RF coil is a planar coil in which a first coil portion including a first linear region and a first nicole portion including a second linear region are connected.
  • the first coil portion and the second coil portion have a conductive wire reversely wound, and the first linear region and the second linear region are arranged in parallel to the extending direction of the groove portion, and the permanent magnet As viewed from the top of the flow path forming surface
  • a region sandwiched between the first straight region and the second straight region may be included in a single groove forming region.
  • the static magnetic field strength becomes maximum at a specific distance from the flow path formation surface in the normal direction of the flow path formation surface.
  • the RF coil is provided between the flow path forming surface of the permanent magnet and the film.
  • An adjustment member may be arranged.
  • a fuel cell comprising the above-described measuring device of the present invention.
  • This fuel cell may include, for example, a solid polymer electrolyte membrane as a membrane. At this time, since the local amount of the protonic solvent in the solid polymer electrolyte membrane can be measured, the distribution of the protonic solvent in the solid polymer electrolyte membrane can be directly obtained.
  • the flow channel is provided on the surface facing the permanent magnet film, for example, a separator provided facing the fuel electrode or oxidant electrode of the fuel cell. At least a part of this can be constituted by a permanent magnet of the measuring device. This simplifies the overall configuration of the fuel cell, while supplying fuel or an oxidant, and even water vapor to the fuel cell electrode, and the amount of local protonic solvent in the polymer electrolyte membrane. Can be measured.
  • the flow path forming surface of the permanent magnet is disposed opposite to the fuel electrode of the fuel cell, and a fuel gas may be supplied to the flow path groove.
  • the flow path forming surface of the fuel cell may be disposed opposite to the oxidant electrode of the fuel cell, and an oxidant gas may be supplied to the flow path groove.
  • a specific shape permanent having a flow path forming surface is provided.
  • a distribution can be formed in the amount of the protonic solvent in the film, and the distribution state can be accurately detected.
  • the amount of protonic solvent in the membrane is adjusted, and multiple echo signals corresponding to this are obtained. It is possible to accurately detect the spatial distribution of the amount of protonic solvent in the membrane.
  • FIG. 1 is a diagram showing a configuration of a permanent magnet in an embodiment.
  • FIG. 2 is a diagram showing a configuration of a permanent magnet in the embodiment.
  • FIG. 3 is a diagram for explaining the measurement result of the z position distribution of the static magnetic field strength formed by the permanent magnet in the embodiment.
  • FIG. 4 is a diagram for explaining the measurement result of the y-position distribution of the static magnetic field strength formed by the permanent magnet in the embodiment.
  • FIG. 5 is a diagram for explaining the measurement result of the X position distribution of the static magnetic field strength formed by the permanent magnet in the embodiment.
  • FIG. 6 is a perspective view for explaining a static magnetic field formed by a permanent magnet in the embodiment.
  • FIG. 7 is a cross-sectional view showing the configuration of the fuel cell in the embodiment.
  • FIG. 8 is a diagram showing a configuration of a planar coil in the embodiment.
  • FIG. 9 is a diagram showing a configuration of a measuring apparatus in the embodiment.
  • FIG. 10 is a cross-sectional view showing the arrangement of permanent magnets, a flat coil, and a sample of the measuring apparatus according to the embodiment.
  • FIG. 11 is a diagram showing a configuration of a measuring apparatus in the embodiment.
  • FIG. 12 is a diagram showing a measurement result of an echo signal in an example.
  • FIG. 13 is a diagram showing the relationship between the distance between the coil and the sample and the echo signal intensity in the example.
  • FIG. 14 is a diagram showing a measurement result of an echo signal in an example.
  • FIG. 15 is a graph showing the relationship between the water content of a sample and T 2 in an example.
  • FIG. 16 is a graph showing the relationship between the moisture content of the sample and the echo signal intensity in the example.
  • FIG. 17 is a diagram showing a measurement result of an echo signal in an example.
  • FIG. 18 is a diagram showing a configuration of a Doub I e-D type coil in an example.
  • FIG. 19 is a diagram showing a configuration of a Doub I e-D type coil in an example.
  • FIG. 20 is a diagram for explaining a magnetic field analysis method in an example.
  • FIG. 21 is a diagram showing magnetic field analysis conditions in the example.
  • FIG. 22 is a diagram showing the ⁇ position distribution of the magnetic field strength in the ⁇ direction of the Doub I e-D type coil in the example.
  • FIG. 23 is a diagram showing contour lines of a magnetic field formed by a Doub I e-D type coil in an example.
  • FIG. 24 is a diagram showing the ⁇ position distribution of the ⁇ direction magnetic field strength of the Doub I e-D type coil in the example.
  • FIG. 25 is a diagram showing magnetic field analysis conditions in the example.
  • FIG. 26 is a diagram showing contour lines of a magnetic field formed by a Doub I e-D type coil in an example.
  • FIG. 27 is a diagram showing a ⁇ position distribution of ⁇ direction magnetic field strength of a Doub I e-D type coil in an example.
  • FIG. 28 is a diagram showing an X-direction magnetic field strength distribution ⁇ X of a Double-D type coil in an example.
  • FIG. 29 is a diagram showing a ⁇ position distribution of ⁇ direction magnetic field strength of a Doub I eD type coil in an example.
  • FIG. 30 is a diagram showing a ⁇ position distribution of ⁇ direction magnetic field strength of a Doub I eD type coil in an example.
  • FIG. 31 is a diagram showing an echo signal reception intensity distribution of a Doustill-D coil in an example.
  • FIG. 32 is a diagram showing a z-position distribution of echo signal reception intensity of a Doub I e-D type coil in an example.
  • FIG. 33 is a diagram showing an echo signal reception intensity distribution of the Doub I e-D type coil in the example.
  • FIG. 34 is a diagram showing a z-position distribution of echo signal reception intensity of the Doub I e-D type coil in the example.
  • FIG. 35 is a diagram showing a z-position distribution of echo signal reception intensity of a Doub I e-D type coil in an example.
  • FIG. 36 is a diagram showing a configuration of a fuel cell in an embodiment.
  • FIG. 37 is a diagram showing a cell configuration of a fuel cell in an embodiment.
  • the amount of the protonic solvent in the film is calculated using a nuclear magnetic resonance (NMR) method.
  • the number density and relaxation time constant can be obtained by detecting the motion of nuclear magnetization as an NMR signal due to the spin resonance phenomenon of a nucleus placed in a magnetic field.
  • the physical quantity corresponding to the atomic number density include the water content in the polymer electrolyte membrane.
  • the relaxation time constant for example, there are T T 2 relaxation time constant, the use of the CPMG method, strongly dependent on the T 2 (CPMG) relaxation time constant on the water content is obtained.
  • the CPMG method is used as an example to explain the case where the excitation vibration magnetic field is applied as a high-frequency pulse sequence.
  • the measuring apparatus of the present invention includes a permanent magnet having a specific shape having a flow channel and an RF detection coil (also simply referred to as "RF coil”) that applies an excitation oscillating magnetic field.
  • RF coil an RF detection coil
  • first specific examples of the permanent magnet and the RF coil constituting the measuring apparatus in the first embodiment and the second embodiment will be shown.
  • the third embodiment a specific configuration of a measuring apparatus in which the permanent magnet and the RF coil are combined will be described.
  • a specific example of a fuel cell including the measuring device described in the third embodiment is shown.
  • FIG. 1A and FIG. 1B are diagrams showing the configuration of the permanent magnet of the present embodiment.
  • Fig. 1 (b) is a partial cross-sectional view of ⁇ _ ⁇ 'in Fig. 1 (a).
  • FIG. 1 (a) and 1 (b) show an example of the shape and dimensions of the permanent magnet 1 1 3; however, the shape and dimensions of the permanent magnet 1 1 3 are not limited to those shown in the figure. .
  • the unit of the dimension attached to the double-sided arrow in Fig. 1 (b) is mm.
  • FIG. 2 is a view showing a permanent magnet manufactured with the dimensions shown in FIG.
  • the permanent magnet shown in FIGS. 1 and 2 is a member made of a magnetic material and applying a static magnetic field to a film to be measured in a protonic solvent amount measuring apparatus.
  • Examples of the material of the permanent magnet 1 1 3 include neodymium, iron, and boron materials such as NEOMAX (registered trademark) manufactured by NEOMAX.
  • the permanent magnet 1 1 3 force is exemplified by a configuration in which blocks made of a plurality of magnetic materials are joined, but the permanent magnet 1 1 3 is a single unit.
  • the structure which consists of these blocks and does not have a junction part may be sufficient.
  • the permanent magnet 1 13 is provided with a flow path forming surface, and the flow path forming surface is provided with a flow path groove 110 1 through which a fluid containing a protonic solvent flows.
  • the film to be measured is provided in parallel to the flow path forming surface of the permanent magnet 1 1 3.
  • the permanent magnets 1 1 3 apply the static magnetic field in the normal direction of the film.
  • the flow path forming surface of the permanent magnet 1 13 corresponds to the top surface of the convex part 103, and the groove part included in the flow path groove 101 corresponds to the concave part 105.
  • the flow path forming surface of the permanent magnet 1 1 3 has a plurality of recesses 1 provided alternately in succession. Including an uneven surface constituted by 0 5 and convex portions 1 0 3.
  • the plurality of convex portions 10 3 and the plurality of concave portions 10 5 all extend in parallel with each other. Both the convex portion 103 and the concave portion 105 extend linearly in one specific direction (the X direction in the figure).
  • top surfaces of the plurality of convex portions 10 3 are all located in the same plane, and the bottom surfaces of the plurality of concave portions 1 0 5 are all parallel to the top surface of the convex portion 10 3. Located in the same plane.
  • FIG. 1 (a) the case where the top surface of the convex portion 103 and the bottom surface of the concave portion 105 are both horizontal to the xy plane is illustrated.
  • the width of the plurality of convex portions 103 (y direction) and the width of the plurality of concave portions 105 are both substantially equal.
  • the permanent magnet 1 1 3 used in the present embodiment has a groove on the opposite side (lower surface side in FIG. 1 (a)) to the formation surface (the upper surface in FIG. 1 (a)) of the projections 1 0 3 and 1 5 5.
  • 1 0 5 a is formed.
  • the groove portion 10 5 a is formed by digging in a direction intersecting with the extending direction of the recess portion 10 5 (y direction in the figure). Further, the groove portion 10 5 a is formed deepest at the center in the extending direction of the recessed portion 10 (X direction in the figure) and shallowest at both end sides.
  • the specific transverse plane of the groove portion 10 5 a (cross section cut perpendicular to the y-axis in the figure)
  • the shape is not particularly limited, but in the present embodiment, this is a triangle.
  • the cross-sectional shape of the groove portion 10 5 a may be a semicircular shape or a parabolic shape.
  • the permanent magnet 1 1 3 having such a configuration When the permanent magnet 1 1 3 having such a configuration is arranged in the space, it is in the plane parallel to the flow path forming surface (the xy plane in the figure) on the upper part of the convex part 10 3 and the upper part of the concave part 1 5. A region having a uniform static magnetic field strength is formed.
  • a region having a uniform static magnetic field strength in a plane parallel to the flow path forming surface is formed along the extending direction of the convex portion 103.
  • the width of the convex portion 103 it is formed over a specific width.
  • a region having a uniform static magnetic field strength in a plane parallel to the flow path forming surface is formed along the extending direction of the concave portion 105, and the concave portion It is formed over a specific width in the width direction of 105. These areas can be used as measurement areas when performing local NMR measurement of the film.
  • a uniform static magnetic field plane is formed in the upper part of the convex portion 103 and the concave portion 105 along the extending direction.
  • a Gauss meter (TM-501 manufactured by KAN ET EC) was used as a measuring device.
  • For the static magnetic field strength only the z-direction component was measured.
  • Figures 3, 4 and 5 show the measured static magnetic field strength (z-direction component) in the z-axis direction (normal direction of the flow path forming surface), y-axis direction (cross-sectional direction of the groove), and X
  • the distribution of the position in the axial direction (extending direction of the groove) was shown.
  • FIGS. 3 (a) and 3 (b) are diagrams illustrating the measurement results of the position distribution of the static magnetic field strength H Q (z-direction component) in the z-axis direction.
  • 4 (a) and 4 (b) are diagrams illustrating the measurement results of the position distribution in the y-axis direction of the static magnetic field strength H Q (z-direction component).
  • the height of the concave portion 1 05 is higher than the height of the concave portion 1 05 on the flow path forming surface.
  • the measurement area can be a position of 1/4 or more of the depth of 05, preferably a position of 1/3 or more.
  • the upper limit of the height of the measurement area is not particularly limited. For example, from Fig. 3 (b), the static magnetic field in the z direction is rapidly increased up to about 1.5 times the depth of the recess 105. Fluctuations can be suppressed.
  • the area where the magnetic field strength becomes maximum is obtained.
  • a zone is formed.
  • the region where the magnetic field intensity is maximum is not formed on the plane of the permanent magnet having no flow channel 10 1, but is a phenomenon unique to the permanent magnet 1 1 3 having the flow channel 1 0 1. .
  • the vicinity of the region where the magnetic field strength at the top of the recess 105 is maximum for example, in the region of the height of 1/3 or more and 3/2 or less of the depth of the recess 105, it is horizontal to the flow path formation surface. Since the amount of change in the static magnetic field strength in the in-plane direction is even smaller, changes in the measured value due to the displacement of the measurement position can be further suppressed when performing NMR measurement of the film.
  • the magnetic field strength is about 0.2 to 0.3 Tes Ia even at a position away from the magnet, for example, z> 1 Omm. As shown in the examples described later, NMR measurement is sufficiently possible with such a magnetic field strength.
  • FIGS. 5 (a) to 5 (c) are diagrams for explaining the measurement results of the position distribution in the x-axis direction of the static magnetic field strength HQ (z-direction component).
  • Fig. 5 (a) shows a cross section of the permanent magnet 1 13 with respect to the extending direction of the convex portion 103 and the concave portion 105.
  • Fig. 5 (b) shows the extending direction of the convex portion 103 and the concave portion 105.
  • a cross section of a permanent magnet 1 1 3 perpendicular to is shown.
  • Fig. 5 (c) is a diagram showing the position distribution in the X-axis direction of the static magnetic field strength HQ (z-direction component).
  • Fig. 5 (c) shows the magnetic field strength in the groove direction. From FIG. 5 (c), it can be seen that the magnetic field strength is almost uniform along the extending direction of both the upper part of the convex part 103 and the upper part of the concave part 105. This is because, as described above, the groove 1 05 a is dug and formed on the surface opposite to the formation surface of the convex portion 103 and the concave portion 105, and the thickness of the permanent magnet 1 13 is set in the X direction (extension of the concave portion 105. Direction) due to being thin at the center and thick at both ends.
  • the static magnetic field strength H 0 was made uniform in the extending direction of the recess 105.
  • the nuclear magnetic resonance frequency of the film at the time of NMR measurement becomes uniform in the extending direction of the groove, that is, in the extending direction of the convex portion 103 and the concave portion 105.
  • FIG. 6 is a perspective view showing the first region 1 07 and the second region 1 0 9 which are NMR measurement smooth with the permanent magnet 1 13 of the present embodiment.
  • a region where the static magnetic field strength is uniform in a plane parallel to the flow path forming surface (first The region 10 7 and the second region 10 9) are formed as cylindrical regions on the upper part of the convex part 103 and the upper part of the concave part 105, respectively.
  • the width of the first region 1007 and the second region 1009 is the position in the z direction as shown in Fig. 4 (b).
  • the first region 1 07 for the region of about 1/4 of the width of the protrusion 1 0 3 on both sides from the center (maximum point) of the protrusion 1 0 3, It can be a region where the spatial non-uniformity of the static magnetic field is small.
  • the spatial nonuniformity of the static magnetic field is about 1/4 of the width of the recess 1 0 5 on both sides from the center (minimum point) of the recess 1 0 5. It can be a small area.
  • the permanent magnet 1 1 3 of this embodiment has a shape with an uneven surface, and the NMR measurement is performed with the uneven surface facing the film in parallel.
  • the permanent magnet 1 1 3 can be incorporated into the fuel cell as a separator (gas flow path). Is possible.
  • the permanent magnet 113 As a separator for the fuel cell, it is possible to measure the amount of the protonic solvent in the electrolyte layer of the fuel cell such as a solid polymer electrolyte membrane.
  • a configuration example of a fuel cell provided with a measuring device having permanent magnets 11 and 13 will be described in more detail in the fourth embodiment.
  • a configuration in which a plurality of recesses 10 5 (grooves) are independently provided on the flow path forming surface of the permanent magnet 1 13 is illustrated.
  • the shape of 1 is not limited as long as a plurality of protrusions 103 and recesses 105 are repeatedly provided in a cross-sectional view, and in a plan view, a plurality of groove portions communicate with each other. There may be. Even in the case where a plurality of grooves are connected, if the permanent magnet has the cross-sectional shape described above with reference to FIGS. 3 to 6, the static magnetic field distribution according to the static magnetic field distribution shown in FIGS. Since it is formed, it can be used as a permanent magnet used to measure the distribution of the amount of protonic solvent in the film.
  • the configuration in which the plurality of flow portions included in the flow channel groove extend in parallel to each other is illustrated, but the planar shape and the planar arrangement of the flow channel are not limited thereto.
  • the configuration of the RF coil used in the measurement apparatus of the third embodiment will be described.
  • the membrane to be measured is a solid polymer electrolyte membrane
  • the membrane to be measured is a solid polymer electrolyte membrane
  • the top surface of the convex portion 103 and the concave portion 1 0 5 A static magnetic field H Q is formed in a direction perpendicular to the bottom surface (z direction, upward in the figure).
  • the NMR measurement is further facilitated along the extending directions, and regions are formed.
  • a planar coil configured to form an oscillating magnetic field for excitation in the first region 10 7 or the second region 1 09 is used as the RF coil.
  • the planar coil forms an oscillating magnetic field for excitation in a direction perpendicular to the static magnetic field, specifically, it hangs in the direction in which the flow path is formed and in the direction in which the groove extends.
  • a case where an excitation oscillating magnetic field having an amplitude in a straight direction is formed will be described as an example.
  • FIG. 8 is a diagram schematically showing the configuration of the planar coil.
  • the number and shape of the planar coil are not limited to this.
  • the planar coil 1 1 4 shown in FIG. 8 includes a pair of coil portions (first coil portion 1 1 9, second coil portion 1 2 1) and is excited in a region sandwiched between the pair of coil portions. Form an oscillating magnetic field.
  • the planar coil 1 1 4 is, for example, a region sandwiched between a pair of coil portions when viewed from the upper part of the flow path forming surface of the permanent magnet 1 1 3, within a single groove portion forming region. Or it is used by arrangement
  • the first coil portion 1 1 9 force is a coil portion including the first linear region 1 23 and the conductive wire is wound in the right-handed direction.
  • the second coil portion 1 2 1 force is the second linear region 1
  • the winding method of the conductive wire in each coil portion is not limited to this. If current flows in the same direction in the first linear region 123 and the second linear region 125, an excitation oscillating magnetic field perpendicular to the linear region and parallel to the coil surface is formed between these linear regions.
  • the planar coil 1 1 4 is of the Doub Ie_D type (also called an 8-shaped coil or a butterfly coil).
  • Doub I e _D type coil has a shape in which a conducting wire is wound in a semicircular shape and two coils face each other, and the two semicircular strings correspond to the straight part, and the strings are arranged parallel to each other Is done.
  • FIG. 8 shows specific dimensions of the planar coil 114 and the LC resonance circuit.
  • a 0.2 mm diameter copper wire is wound in 5 semi-circles each having a diameter of 12 mm, and the strings are arranged in parallel at intervals of 1.2 mm.
  • three copper wires are shown schematically.
  • the resonance frequency of this coil is, for example, 13.07 MHz.
  • the Q value of the chlority factor of the manufactured coil is 25.
  • the dimensions and number of turns of the illustrated planar coil 1 14 are examples designed according to the dimensions of the permanent magnet 1 1 3 shown in FIG. 1, and are not limited to these dimensions.
  • the region near the symmetry axis of the pair of coil parts is a more preferable region for NMR measurement.
  • planar coil 1 1 4 of this embodiment By using the planar coil 1 1 4 of this embodiment in combination with the first embodiment, a region where the static magnetic field is uniform in the plane (first region 1 0 7, second region 1 0 9 ), And an oscillating magnetic field for excitation can be reliably formed in these regions. Then, a film is arranged on the upper part of the first area 10 07 or the second area 10 09, and the first signal 10 07 or the upper area of the second area 10 09 is used as a measurement area to output an eco signal. Acquiring can improve the accuracy of NMR measurement of the film.
  • the groove 1 0 5 a is dug on the opposite surface (lower surface) side of the formation surface (upper surface) of the protrusion 1 0 3 and the recess 1 0 5 as described above.
  • the static magnetic field strength in the extending direction (X direction) of the recess 1 0 5 is made uniform (see Fig. 1 (a) and Fig. 5 (c)). See).
  • the static magnetic field strength is made uniform throughout the detection region of the planar coil 114, and the resonance frequency of the proton in the sample becomes a more uniform frequency throughout the detection region. Therefore, the NMR signal, which is the sum of the vectors, increases, and the SN ratio can be improved.
  • the structure is suitable for multipoint measurement in the thickness direction of the film.
  • multiple planar coils 1 1 4 are stacked
  • the distribution of the amount of protonic solvent in the thickness direction at a specific location in the plane of the membrane can be measured. It is also possible to perform measurement at different positions in the thickness direction of the film by using one planar coil 1 14.
  • the resonance frequency in NMR measurement changes depending on the strength of the static magnetic field. With this magnet, the magnetic field strength changes in the direction of the film thickness, and the resonance frequency changes accordingly. NMR measurement can be performed by selecting the measurement position in the thickness direction of the film according to the difference in frequency. This difference in resonance frequency can also suppress the interference of NMR signals.
  • planar coils 1 1 4 are arranged in the first region 1 0 7 or the second region 1 0 9, multipoint measurement can be performed in the same static magnetic field.
  • This configuration is also suitable for measuring the distribution in the in-plane direction, and for measuring the amount of the protonic solvent multiple times in the region where the film faces a specific recess 105.
  • a planar coil 1 1 4 is arranged in each of these. Then, signal interference can be more effectively suppressed.
  • the permanent magnet 1 1 3 when used as a separator of a fuel cell, a polymer electrolyte membrane and a separator (the gas diffusion layer is on the separator side) It is desirable to sandwich an RF detection coil between them.
  • a cylindrical shape such as a solenoid type coil has a three-dimensional shape and cannot be sandwiched in the gap.
  • the RF detection coil is planar (sheet-like), it can be easily inserted into the gap.
  • the planar coil 1 1 4 as the RF coil, even when the solid polymer electrolyte membrane is measured using the permanent magnet 1 1 3 as the separator of the fuel cell, It is easy to incorporate, and the overall size of the fuel cell can be suppressed.
  • planar coil 1 1 4 is a Doub I e _ D type coil having two half-moon-shaped coil portions
  • the planar coil 1 1 4 is First coil part 1 1 9 and second straight line with first straight region 1 2 3
  • the second coil portion 1 2 1 including the region 1 2 5 is included, and the conductive wire of these coil portions may be configured to be reversely wound, and the planar shape of the coil portion is not limited to the half-moon shape.
  • the planar shape of the two coil portions may be a polygon such as a square, a rectangle, or a triangle.
  • planar coil 1 14 is not particularly limited in size as long as it is configured to apply an excitation oscillating magnetic field to a part of the film, but can be made smaller than the film to be measured, for example. .
  • the planar coil 1 1 4 can be made smaller than the flow path forming surface of the permanent magnet 1 1 3, for example. More specifically, in the cross-sectional view of the extending direction of the groove portion of the permanent magnet 1 1 3, the width of the planar coil 1 1 4 is set to the convex portion 10 3 and the concave portion 1 0 5 of the permanent magnet 1 1 3, respectively. It may be larger than the sum of the width of each piece.
  • the width of the planar coil 1 1 4 may be smaller than the sum of the widths of the concave portion 1 0 5 and the convex portion 1 0 3, or may be made smaller than the width of one convex portion 1 0 3. May be. In this way, when the planar coil 1 1 4 is placed between the flow path forming surface of the permanent magnet 1 1 3 and the film, the z direction between the planar coil 1 1 4 and the permanent magnet 1 1 3 and the film It is possible to more reliably regulate the interval.
  • the present embodiment relates to a measuring apparatus including the permanent magnet 1 1 3 described in the first embodiment and the RF coil (planar coil 1 1 4) described in the second embodiment.
  • FIG. 9 is a diagram showing a configuration of the measurement apparatus of the present embodiment.
  • the measuring device 100 shown in FIG. 9 is a device that locally measures the amount of the protonic solvent at a specific location in the film using the nuclear magnetic resonance method.
  • the proton solvent is water
  • Permanent magnet that applies a static magnetic field in a specific direction to the film 1 1 5 to be measured 1 1 3
  • a vibrating magnetic field for excitation is applied in a direction perpendicular to the static magnetic field to the film 1 1 5
  • an echo signal corresponding to the oscillating magnetic field for excitation, a planar coil 1 1 4, and
  • the permanent magnet 1 1 3 is made of a magnetic material.
  • the film 1 1 5 is disposed in parallel to the flow path forming surface of the permanent magnet 1 1 3.
  • the permanent magnet 1 1 3 applies a static magnetic field in the thickness direction of the film 1 1 5. With this static magnetic field applied, a high frequency pulse for excitation is applied to the film 1 15 and the T 2 relaxation time constant is measured.
  • planar coil 1 1 4 applies an excitation high-frequency pulse.
  • 14 is the Doub Ie_D type RF detection coil described in the second embodiment.
  • the arrangement of the force planar coil 1 1 4 in the example in which the two linear regions of the planar coil 1 1 4 are arranged on the upper part of the recess 1 0 5 is not limited to this. You may arrange
  • FIG. 10 is a cross-sectional view showing the arrangement of the permanent magnet 1 1 3, the planar coil 1 1 4, and the film 1 1 5 in more detail in the measuring apparatus 1 100 shown in FIG.
  • the planar coil 1 1 4 is disposed above the flow path forming surface of the permanent magnet 1 1 3.
  • the permanent magnet 1 1 3 has a convex portion 1 0 3 and a planar coil 1 1 4, and the planar coil 1 1 4 and a solid An interval adjusting member (first spacer 1 2 7, second spacer 1 2 9) with a specific thickness made of a non-magnetic material is placed between the polymer electrolyte membrane 1 1 7 Has been.
  • Permanent magnet 1 1 3 static magnetic field H o direction and Doub I e _ D type The direction of the oscillating magnetic field created by the coil (planar coil 1 1 4) is perpendicular
  • the echo signal intensity changes when the distance in the z direction from the solid polymer electrolyte membrane 1 17 is changed. This is because the intensity distribution of the oscillating magnetic field H and the reception sensitivity of the coil change depending on the distance.
  • the maximum echo signal intensity is obtained when the distance is about 1 mm. is there.
  • the first spacer 1 having a specific thickness between the permanent magnet 1 1 3 and the planar coil 1 1 4 is used. By placing 27, keep them at specific intervals. Further, by arranging a second spacer 1 29 between the planar coil 1 14 and the solid polymer electrolyte membrane 1 17, these are maintained at a specific interval. By using these spacers to adjust the relative position (z direction) of the uneven surface of the permanent magnet 1 1 3, the planar coil 1 1 4 installation surface and the solid polymer electrolyte membrane 1 1 7, the solid polymer By precisely adjusting the measurement position in the thickness direction of the electrolyte membrane 1 17, the reception sensitivity of the echo signal can be improved in the measurement region. Therefore, local T 2 measurement of the solid polymer electrolyte membrane 117 can be performed with high sensitivity and high accuracy.
  • the third spacer is formed on the upper portion of the convex portion 103 where the planar coil 11 14 is not disposed.
  • 1 3 5 and a bead-like spacing adjusting member (not shown) in the gap 1 3 7 formed between the third spacer 1 3 5 and the solid polymer electrolyte membrane 1 1 7 May be filled. In this way, the distance between the permanent magnet 1 1 3 and the solid polymer electrolyte membrane 1 1 7 can be adjusted more precisely, and the solid polymer electrolyte membrane 1 1 7 can be held in that state.
  • the thickness of the third spacer 1 3 5 is the same as the thickness of the first spacer 1 2 7, the second spacer 1 2 9 and the planar coil 1 1 4. More specifically, the thickness is set to be approximately equal to the total thickness of the first spacer 1 27 and the second spacer 1 29.
  • the arrangement shown in FIG. 10 is, for example, a solid polymer electrolyte membrane (PEM) for a fuel cell is held by a separator (permanent magnet 1 1 3), and Doub I 6_0 type in the gap between the two.
  • PEM solid polymer electrolyte membrane
  • the measuring device 100 is also suitably used for local moisture measurement of a solid polymer electrolyte membrane of a fuel cell.
  • the measuring apparatus 100 of the present embodiment can be used as an apparatus for evaluating the local water content of a membrane such as a solid polymer electrolyte membrane.
  • the planar coil 1 1 4 may be singular or plural. If the number is plural, it is possible to measure the moisture content distribution in the membrane 1 1 5. In this case, if it is arranged two-dimensionally along the surface of the membrane 115, the two-dimensional moisture content distribution on the membrane surface can be obtained. In addition, if three-dimensionally arranged in the membrane 1 15, the three-dimensional moisture content distribution in the membrane can be obtained.
  • the oscillating magnetic field (exciting oscillating magnetic field) applied by the planar coil 1 1 4 is R
  • the excitation high-frequency RF transmitted from the RF oscillator 102 is modulated by the modulator 104 based on the control by the pulse control unit 108 and becomes a pulse shape.
  • the generated RF pulse is amplified by the RF amplifier 106 and then sent to the planar coil 1 14.
  • the planar coil 1 14 applies this RF pulse to a specific part of the film.
  • the planar coil 1 14 detects the echo signal of the applied RF pulse. This echo signal is amplified by the preamplifier 1 1 2 and then sent to the phase detector 1 10.
  • the phase detector 1 1 0 detects this echo signal and sends it to the A / D converter 1 1 8.
  • a / D converter 1 1 8 After the A / D conversion of the echo signal, it is sent to the calculation unit 130.
  • the switch unit 1 61 is provided at a branching unit that connects the planar coil 1 14, RF signal generation unit, and echo signal detection unit.
  • the RF signal generation unit includes an RF oscillator 102, a modulator 104, and an RF amplifier 106, and generates an RF signal that causes the planar coil 1 14 to generate an oscillating magnetic field for excitation.
  • the echo signal detection unit is composed of a preamplifier 1 1 2, a phase detector 1 1 0, and an A / D converter 1 1 8, and detects the echo signal acquired by the planar coil 1 1 4, Is sent to the arithmetic unit 130.
  • the switch portion 1 61 is a planar coil 1 1 4? 3 ⁇ 4 “Signal generator (RF amplifier)
  • the switch unit 1 61 serves as such a “transmission / reception switching switch”.
  • the switch portion 1 61 By providing the switch portion 1 61 at the branch portion, the loss of the excitation high-frequency pulse signal applied from the planar coil 1 14 to the membrane 1 15 is reduced. As a result, the 90 ° pulse and 1 It becomes possible to control the pulse angle of 80 ° pulse accurately. Accurate control of the pulse angle is an important technical problem for reliably obtaining the compensation effect in the pulse echo method. In this embodiment, such a problem is solved by the arrangement of the switch unit 161.
  • the planar coil 1 14 for local measurement is miniaturized, and the reduction of noise during N MR reception is an important factor for ensuring the accuracy of measurement.
  • the noise that enters the preamplifier 1 1 2 mainly includes an RF wave transmission system, and “RF wave leakage” or “large” from the RF amplifier 1 06 that amplifies the excitation pulse. There is noise generated by power amplifiers.
  • the excitation high frequency pulse and the detection of the echo signal have been described above. However, these can be realized by an LC circuit including a small coil (Fig. 8).
  • the coil part (inductance part) of the resonance circuit is a small RF coil as described above.
  • the nuclear magnetic resonance (NMR) method can measure atomic density and spin relaxation time constant by detecting the motion of nuclear magnetization as an NMR signal by the spin resonance phenomenon of a nucleus placed in a magnetic field.
  • the spin resonance frequency in a magnetic field of 1 Tes Ia is about 43 MHz (this frequency band is called radio frequency), and in order to selectively detect that frequency band with high sensitivity, it is shown in Fig. 8.
  • Such an LC resonant circuit is used.
  • the high frequency pulse for excitation applied by the planar coil 1 1 4 to the film 1 1 5 is, for example,
  • the pulse sequence can consist of In order to clearly grasp the correlation between the T 2 relaxation time constant and the amount of moisture in the film, it is important to properly apply the oscillating magnetic field. By using the pattern as described above, it is possible to clearly grasp the correlation between the 2 relaxation time constant and the amount of moisture in the film.
  • the planar coil 1 14 it may be difficult to adjust the excitation pulse intensities (a) and (b).
  • the region to be measured that is, the region surrounded by the planar coil 1 14, there is a difference in the excitation method between the central portion and the peripheral portion, and the whole becomes a uniform excitation angle.
  • the pulse control unit 1 08 force In addition to the 90 ° pulse (a), another sequence is executed at a time just before the 90 ° pulse (a), plus the step of applying the 180 ° pulse. Then, by comparing the behavior of the decay curves of the 180 ° pulse (b) corresponding to these two sequences, the excitation pulse intensities of the 90 ° pulse (a) and the 180 ° pulse (b) Whether or not is accurate. As a result, even if the excitation pulse intensity is deviated due to an abnormality in the device, the abnormality can be detected before the measurement is performed, and the measurement value can be made more accurate.
  • the calculation unit 1 30 calculates the T 2 relaxation time constant from the intensity of the echo signal, and calculates the water content at a specific location in the film from the calculated ⁇ 2 relaxation time constant.
  • T 2 when relaxation time constant is calculated the data is sent to a solvent amount calculating unit 1 2 4.
  • the solvent amount calculation unit 1 2 4 accesses the calibration curve table (storage unit) 1 2 6 and acquires calibration curve data corresponding to the membrane.
  • the solvent amount calculation unit 1 24 uses the obtained calibration curve data and the 2 relaxation time constant calculated as described above to calculate the amount of water in the film.
  • the calculated water content is presented to the user by the output unit 1 3 2. There are no particular restrictions on the type of presentation, including display on the display, printer output, and file output.
  • a planar coil is formed inside the film, on the film surface, or in the vicinity of the film.
  • Multiple 1 1 4 can also be arranged. Thereby, it is configured to be able to apply the excitation oscillating magnetic field and acquire the echo signal corresponding to the excitation oscillating magnetic field to a plurality of locations on the membrane.
  • Solvent amount distribution calculation section 1 2 8 Based on the water content at the place, the water content distribution in the membrane is calculated. The output unit 1 32 outputs this moisture content distribution.
  • a film 1 15 is placed in parallel with the flow path forming surface of a permanent magnet 1 1 3 with a flow channel groove, and a specific location in the film 1 1 5 is detected using a nuclear magnetic resonance method.
  • a method for locally measuring the amount of a protic solvent comprising the following steps. First, a static magnetic field is applied in the thickness direction of the film 1 1 5 by the permanent magnet 1 1 3 while flowing the fluid containing the above-mentioned protonic solvent in the flow channel of the permanent magnet 1 1 3 (step (S ) 1 02). In this state, an excitation oscillating magnetic field is sequentially applied several times to a part of the film 1 15 placed in a static magnetic field using an RF coil (planar coil 1 1 4).
  • an excitation high-frequency pulse is applied to the membrane.
  • the excitation high-frequency pulse is a pulse sequence including a plurality of pulses, and an echo signal group corresponding to the pulse sequence is acquired. Is preferred. By doing so, it is possible to accurately determine the T 2 relaxation time constant.
  • the pulse sequence preferably comprises the following (a) and (b).
  • the CPMG method is an example of a method for providing such a pulse sequence.
  • the magnetization vector is first tilted in the positive direction of the vertical axis by a 90 ° pulse, and then 1 80 ° excitation pulse is irradiated from the outside in the “axial direction” after a period of time. Invert the vector “with the ⁇ axis as the symmetry axis”. As a result, after two hours, the magnetization vector converges on the “positive direction” of the heel axis, and an echo signal with a large amplitude is observed.
  • the magnetization vector was irradiated with an external 1 80 ° excitation pulse in the “axis direction” and converged again on the “positive direction” of the axis, and a large amplitude after 4 hours.
  • an echo signal with Furthermore, continue to irradiate 1 80 ° pulse at the same two intervals.
  • the peak intensity of the even-numbered echo signals of 2, 4, 6, 6 is extracted, and fitted with an exponential function to calculate ⁇ 2 (lateral) relaxation time constant by the CPMG method. be able to.
  • step 106 measure the relaxation time constant ⁇ 2 by using the spin echo method.
  • p is the density distribution of the target nuclide as a function of position (X, y, z)
  • TR is the 90 ° excitation pulse repetition time (from about 10 Oms to 10 seconds)
  • TE is the echo Time (2 t, about 1 ms to 10 Oms)
  • A is a constant that represents RF coil detection sensitivity and device characteristics such as amplifier.
  • Step 1 08 the moisture content is calculated from the relaxation time constant.
  • the water content and the T 2 relaxation time constant in the film with a positive correlation.
  • T 2 relaxation time constant is increased. Since this correlation varies depending on the type and form of the membrane, it is desirable to prepare a calibration curve for the same type of membrane as the measurement target membrane whose moisture concentration is known in advance. That is, the water content in pairs to a plurality of known standard samples film measurement of the relationship between water content and the T 2 relaxation time constant, it is desirable to seek beforehand roughness a calibration curve showing the relationship.
  • the amount of moisture in the film can be calculated from the measured value of ( 2) relaxation time constant.
  • permanent magnets 1 1 3 and planar coils 1 1 4 are used in specific shapes, and these are arranged in a specific positional relationship with the film 1 15.
  • a fluid containing a protonic solvent is caused to flow into the recesses 10 5 of the permanent magnets 1 1 3 to form a distribution in the amount of the protonic solvent in the film 1 15, and the distribution thus formed is planar.
  • Coil 1 1 4 can be measured. It is also possible to adjust the amount of the protonic solvent in the membrane 1 15 and measure the spatial distribution of the amount of the protonic solvent in the membrane 1 15 with the planar coil 1 14.
  • the moisture content distribution in the film 115 can be measured on the spot. It is also possible to evaluate the water dispersion behavior in the in-plane direction of the membrane 1 15.
  • the measurement region of the membrane 1 15 is included in the first region 1 07 and the second region 1 09, the local moisture content of the membrane 1 15 can be measured more. It can be performed with higher accuracy and good reproducibility.
  • the first region 10 07 that is the upper region of the convex portion 103 is perpendicular to the flow path forming surface of the permanent magnet 11 13. In the direction (z direction), there is a position where the static magnetic field becomes maximum. If measurement is performed at such a position, fluctuations in measurement values due to misalignment of the measurement area can be suppressed, and more accurate measurement can be performed.
  • a magnetic field is applied only to a position and place where measurement is desired with respect to a thin sheet-like film 1 15 such as a polymer electrolyte, and a planar shape is formed in the gap between the magnet and the film.
  • the local moisture content can be measured using an RF detection coil.
  • local measurement can be performed in a shorter time than MRI measurement.
  • the NMR sensor in the measuring apparatus 100, can be made compact, so that the restriction on the installation location of the apparatus is eased. In addition, the price of equipment can be reduced. In addition, if the unitary device is a combination of the planar coil 1 1 4 and the permanent magnet 1 1 3, there is no need to align the two, and measurement can be performed easily.
  • the permanent magnets 11 and 13 can be downsized. Here, in FIG. 9 and FIG. 11, the force that illustrates the configuration in which the uneven surface of the permanent magnet 1 1 3 is larger than the film 1 1 5, the permanent magnet 1 1 3 has a static magnetic field at the measurement location of the film 1 1 5. This is not limited to the case where the uneven surface is larger than the film 1 15.
  • a small magnet is used as a permanent magnet and a magnetic field is applied only to a part of the film, and an NMR signal can be received by a small RF detection coil only from the region where the magnetic field is applied, for example, the following advantages can be obtained. Is possible.
  • the dimensions of the membrane are arbitrary and are not limited to magnet dimensions.
  • the magnet shape can be arbitrarily set. Therefore, for example, when applied to a fuel cell, a structure in which a gas flow path portion is incorporated in a magnet can be obtained.
  • the local water content of the membrane can be measured at the position to be measured.
  • the NMR sensor can be made more compact, easier to install, and less expensive.
  • FIG. 11 is a diagram showing another configuration of a measuring apparatus including permanent magnets 1 1 3 and planar coils 1 1 4.
  • a large magnet is also incorporated into the actual fuel cell and used as a monitoring device.
  • the magnet is too large to be mounted and cannot be a practical sensor.
  • the measuring apparatus 100 described above in the third embodiment has a structure in which the concave portion 105 of the permanent magnet 11 13 can be used as a gas flow path portion. Therefore, in the present embodiment, the permanent magnet 113 is incorporated into the fuel cell device as a part of the separator of the fuel cell so that the moisture content of the membrane 1 15, that is, the solid polymer electrolyte membrane 1 17 can be measured.
  • the measuring device 100 By incorporating the measuring device 100 into the fuel cell, it is possible to constantly monitor the water content of the polymer electrolyte membrane of the fuel cell and control so that the polymer electrolyte membrane can always maintain high conductivity. become able to. For this reason, it is possible to control the operation of the fuel cell so that the power generation efficiency of the fuel cell is maintained high.
  • FIG. 36 is a diagram showing the configuration of the fuel cell of the present embodiment.
  • the fuel cell 1 3 1 shown in FIG. 3 includes a measuring device 1 0 0, a cell 1 3 3, and an oxidant gas supply unit 3 2 for supplying an oxidant gas (for example, oxygen or air) to the cell 1 3 3, Fuel gas supply unit 3 3 for supplying fuel gas (for example, hydrogen gas) to the cell 1 3 3 and oxidant gas and fuel gas supply unit 3 supplied from the oxidant gas supply unit 3 2 to the cell 1 3 3 It has a steam mixing section 3 4, a steam mixing section 3 5, and a control section 3 6 that mix steam with fuel gas supplied from 3 toward the cells 1 3 3.
  • oxidant gas for example, oxygen or air
  • Fuel gas supply unit 3 3 for supplying fuel gas (for example, hydrogen gas) to the cell 1 3 3 and oxidant gas and fuel gas supply unit 3 supplied from the oxidant gas supply unit 3 2 to the cell 1 3 3
  • It has a steam mixing section 3 4, a steam mixing section 3 5, and a control section 3 6 that mix steam with fuel gas supplied from 3 toward the cells 1 3 3.
  • FIG. 37 is a cross-sectional view showing a configuration of cell 1 33 of fuel cell 1 31 shown in FIG.
  • Cell 1 3 3 is a solid polymer electrolyte membrane 1 1 7 that is a sample to be measured, and a solid Polymer electrolyte membrane 1 1 7 Catalyst layer 3 1 1 A and catalyst layer 3 1 1 B provided on both sides, Porous diffusion layer 3 1 2 A and diffusion layer 3 1 2 B, Separator 3 1 3 A and a separator 3 1 3 B.
  • the fuel electrode 3 1 4 is composed of the catalyst layer 3 1 1 A and the diffusion layer 3 1 2 A, and the oxidant electrode 3 1 is composed of the catalyst layer 3 1 1 B and the diffusion layer 3 1 2 B. 5 is configured.
  • a groove serving as a fuel gas flow path is formed in the separator 3 1 3 A.
  • a fuel gas containing water vapor is supplied to the flow path groove of the separator 3 1 3 A as a fluid containing a protonic solvent.
  • the separator 3 1 3 B is formed with a groove serving as a flow path for the oxidizing gas.
  • An oxidant gas containing water vapor is supplied to the flow path groove of the separator 3 1 3 B as a fluid containing a protonic solvent.
  • the flow path forming surface of the permanent magnet 1 1 3 is disposed opposite to the fuel electrode 3 1 4 of the fuel cell 1 3 1 and fuel gas is supplied to the recess 1 0 5 or the fuel cell 1 3 1
  • the oxidant gas is supplied to the recesses 10 5 so as to be opposed to the oxidant electrodes 3 15.
  • the separator 3 1 3 A or the separator 3 1 3 B may be composed of a permanent magnet 1 1 3, or the permanent magnet 1 1 3 may be a separator 3 1 3 A or a separator.
  • 3 1 3 May constitute part of B.
  • the oxidant gas supply unit 3 2 supplies oxidant gas to the cells 1 3 3. Further, the fuel gas supply unit 3 3 supplies fuel gas to the cells 1 3 3. Between the oxidant gas supply unit 3 2 and the cells 1 3 3, a water vapor mixing unit 3 4 is provided. In the water vapor mixing unit 3 4, water vapor is generated and mixed with the oxidant gas supplied from the oxidant gas supply unit 3 2 toward the cell 1 3 3. The oxidant gas thus mixed with the water vapor is supplied to the cell 1 3 3. Similarly, the water vapor mixing unit 3 5 is provided between the fuel gas supply unit 3 3 and the cell 1 3 3. It has been. In this steam mixing section 35, steam is generated and fuel The fuel gas supplied from the gas supply unit 3 3 toward the cell 1 3 3 is mixed with water vapor. Fuel gas mixed with water vapor is sent to cells 1 3 3.
  • the solid polymer electrolyte membrane 1 1 7 of the cell 1 3 3 is wetted by mixing the water vapor with the oxidant gas and the fuel gas.
  • the control unit 36 is connected to the measuring device 100, the steam mixing unit 34, and the steam mixing unit 35.
  • control unit 36 the measurement result of the moisture content from the measuring device 100 and the distribution of the moisture content are obtained, and based on this measurement result, the steam mixing unit 34 and the steam mixing unit 35 generate the The water vapor mixing unit 34 and the water vapor mixing unit 35 are controlled so as to adjust the amount of water vapor supplied to the cells 13 3.
  • water is generated by the reaction of hydrogen ions and oxygen gas on the oxidizer electrode 3 1 5 side. Therefore, the water content in the solid polymer electrolyte membrane 1 17 may be excessive, particularly on the oxidant electrode 3 15 side. If the amount of water is excessive, water will aggregate in the flow path of the separator 3 1 3 B, impeding the flow of oxidant gas, which may reduce power generation efficiency.
  • the control unit 36 obtains the moisture content distribution from the measuring device 100 and determines whether the moisture content value in the obtained distribution is within a predetermined range. That is, it is determined whether or not the solid polymer electrolyte membrane 1 17 is in an appropriate wet state. When it is determined that the predetermined range is exceeded, the control unit 36 requests the water vapor mixing unit 34 or the water vapor mixing unit 35 to reduce the amount of water vapor generated.
  • the control unit 3 6 When it is determined that the moisture content in the moisture content distribution obtained from the measuring device 100 is out of the predetermined range and the moisture content is low, the control unit 3 6 The mixing unit 3 4 or the water vapor mixing unit 3 5 is requested to increase the amount of water vapor generated to prevent the solid polymer electrolyte membrane 1 1 7 from drying.
  • control unit 36 adjusts the water vapor generation amount of both the water vapor mixing unit 34 and the water vapor mixing unit 35, and the water vapor supply amount to the cell 13 33.
  • the present invention is not limited thereto, and for example, only the amount of steam generated in the steam mixing unit 35 and the amount of steam supplied to the cell 13 3 may be adjusted.
  • the permanent magnet 1 1 3 can be used as a separator, so that the solid polymer electrolyte membrane 1 1 7 The local moisture content distribution can be measured. Since the water content distribution in the solid polymer electrolyte membrane 1 1 7 can be measured in-situ, it is possible to control to improve the battery operating efficiency.
  • the amount of water in the solid polymer electrolyte membrane 1 1 7 at the top of the recess 10 5 is measured, the amount of water in the membrane in the vicinity of the region where fuel or oxidant is supplied into the membrane can be measured in real time. .
  • the diffusion state of the protonic solvent supplied from the channel groove can be grasped.
  • an RF detection coil that applies a magnetic field only to the position and location where measurement is desired is installed without significantly changing the overall shape of the battery. It needs to be possible.
  • the permanent magnet 1 1 3 is used as a separator, so that the solid polymer electrolyte membrane 1 1 7 force is arranged in parallel to the separator surface and the separator Located in the vicinity.
  • the configuration is suitable for the measurement of the solid polymer electrolyte membrane 1 17 disposed in the magnetic field formed in the vicinity of the flow path forming surface of the separator.
  • a planar coil 1 1 4 as the RF coil, the coil can be easily laminated at a predetermined position near the surface of the solid polymer electrolyte membrane 1 1 7. It is possible to incorporate a device for measuring the water content without significantly changing the thickness.
  • the configuration of the permanent magnet 1 1 3 and the planar coil 1 1 4 is adapted to the thin sheet-shaped solid polymer electrolyte membrane 1 1 7. It becomes possible to measure the local water content of the membrane at the position to be measured.
  • the magnetic field is applied only to a part of the apparatus, restrictions on the apparatus material that can be used are alleviated, and it is not necessary to use all of the apparatus as a non-magnetic material. It has a suitable configuration.
  • the planar coil 1 1 4 is applied to the surface of the solid polymer electrolyte membrane 1 1 7 on the fuel electrode 3 1 4 side and the surface of the oxidant electrode 3 1 5 side, respectively.
  • grasp the water content near the surface on the fuel electrode 3 1 4 side and the surface near the surface on the oxidizer electrode 3 1 5 side and grasp the relationship between the water content near the surface of each electrode and the power generation efficiency. It can also be done. This makes it possible to determine whether the supply of water vapor from either the fuel electrode 3 1 4 side or the oxidant electrode 3 1 5 side is effective for power generation efficiency.
  • the fuel cell 1 3 1 of the present embodiment has obtained useful data for searching for the cause of the decrease in power generation efficiency that occurs when the cell 1 3 3 is operated for a long time. Can be provided from the perspective of
  • FIG. 7 is a cross-sectional view showing a configuration of a stack type fuel cell including a plurality of cells including the solid polymer electrolyte membrane 1 1 7 a and the solid polymer electrolyte membrane 1 1 7 b.
  • the permanent magnet 1 1 3 force is provided as the outermost separator.
  • the permanent magnet 1 1 3 is provided opposite to the endmost cell (solid polymer electrolyte membrane 1 1 7 b) of the fuel cell stack, and the permanent magnet 1 1 3 is solid at the convex portion 1 0 3.
  • the polymer electrolyte membrane 1 1 7 b is held, and fuel gas or oxidant gas flows into the recess 1 0 5.
  • a separator 1 1 1 is a normal separator that does not have a permanent magnet 1 1 3.
  • the magnetic field strength is about 0.2 to 0.3 TesIa even at a position away from the magnet (z> 1 Om m). With this magnetic field strength, NMRR measurement is sufficiently possible. Therefore, even if a magnet is placed at the extreme end of the fuel cell stack, a magnetic field is formed even inside the stack. Moreover, since the static magnetic field strength gradually decreases as the distance increases, the resonance frequency also decreases as the distance from the magnet increases. If the resonance frequency is different, interference of excitation pulses in a plurality of RF coils is less likely to occur.
  • the use of the fuel cell of the present invention is not particularly limited.
  • it may be used not only as a battery but also as an evaluation device for the solid polymer electrolyte membrane 1 17.
  • the measuring apparatus 100 includes a plurality of planar coils 1 1 4 and a plurality of planar coils 1 1 4 force films 1 1 5 And an echo signal corresponding to the oscillating magnetic field for excitation is acquired, and the amount of protonic solvent at a plurality of locations of the solvent amount calculation unit 1 2 4 force membrane 1 1 5 is calculated. Also good.
  • the membrane By arranging planar coils 1 1 4 at multiple locations on the membrane 1 1 5 and measuring the amount of protonic solvent, the membrane It becomes possible to measure the distribution of the amount of 1 5 proton solvent in a shorter time. At this time, if a plurality of planar coils 1 1 4 are arranged on one first region 10 7 described above with reference to FIG. 6 or one second region 1 0 9, the film thickness direction can be increased. Suppresses the deviation of the static magnetic field intensity and enables more accurate multipoint measurement.
  • T 2 do not depend sensitivity of the RF coil, the magnification of the amplifier, the apparatus configuration of the filter one characteristics, Ri by the calculating the pro ton solvent amount in the film from the T 2, pro tons solvent The amount can be calculated more easily. Further, when calculating the amount of the protonic solvent from the signal intensity, a calibration curve for associating the signal intensity with the amount of the protonic solvent may be obtained in advance by an experiment in accordance with the configuration of the measuring apparatus.
  • a gas flow path is attached to the magnet, a magnet with a gas flow path that can be incorporated into a fuel cell device is used as part of the fuel cell separator, and it is suitable for thin sheet polymer electrolyte membranes.
  • the I e _ D type RF detection coil can measure the local water content of the membrane at the position (depth) to be measured.
  • a gas flow path magnet and a Doub Ie_D type coil are installed and measured at the position or location where the fuel cell is to be measured, it is only necessary to apply a magnetic field only to that location. This eliminates the need for a device other than the magnetic field application position to be made of a non-magnetic material, so that the NMR sensor can be applied to a more practical fuel cell device.
  • the NMR sensor can be made more compact, easier to install, and less expensive.
  • an integrated device combining an RF detection coil and a magnet is used, positioning of the two is unnecessary and measurement can be performed easily.
  • the water content of the polymer electrolyte membrane of the fuel cell can be constantly monitored and controlled so that it can always maintain high conductivity. It is possible to maintain high power generation efficiency.
  • the sample to be measured may be in the form of a membrane.
  • the sample is not limited to a solid sample as long as it is in a film form, and may be, for example, a liquid containing a protonic solvent filled in a space having a predetermined thickness. Further, the sample is not limited to a film made of a solid polymer electrolyte or the like, and for example, a predetermined layer such as a catalyst layer may be formed on one side or both sides of the membrane.
  • a predetermined layer such as a catalyst layer may be formed on one side or both sides of the membrane.
  • T 2 (CPMG) values of samples A to C shown below were measured by the CP MG method using the measurement apparatus (third embodiment) shown in FIG.
  • the permanent magnet shown in FIG. 2 was used.
  • the material of the permanent magnet was ⁇ ⁇ 01 ⁇ 1 Yawata Corporation ⁇ —44 ⁇ .
  • the sample was prepared according to the following procedure. First, two pieces of cover glass (dimensions 18 mm x 18 mm, thickness 0.1 2 mm) were bonded with a gap of 0.5 mm to produce a container. Water was poured into the container and the container was sealed. The dimensions of the water part are 15 mm X 15 thickness 0.5 mm. This sample is Also called “0.5 mm thick water sample”.
  • a 0.5 mm thick water sample was regarded as PEM, and placed at the position of the solid polymer electrolyte membrane (PEM) 1 17 having the arrangement shown in FIG. Specifically, a Doub Ie_D type coil was placed on a permanent magnet with a gas flow path, and a “0.5 mm thick water sample” was placed on it.
  • PEM solid polymer electrolyte membrane
  • N MR measurement parameters were as follows.
  • the 90-degree excitation pulse repetition time (TR) is 5 seconds
  • the 90-degree excitation pulse dummy count is 4
  • the NMR signal integration count is 64
  • the resonance frequency is 13.07 MHz.
  • the temperature of the 0.5mm thick water sample was about 25 ° C.
  • C PMG measurement was performed by changing the distance between the Doub I e _ D type RF detection coil and the 0.5 mm thick water sample in 0.5 mm increments, and the relationship with the echo signal intensity was obtained. The results are shown in Figure 13.
  • Figure 13 shows that the echo signal intensity is maximum when the distance (gap) between the coil and the sample is 1 mm. Since the sample thickness is 0.5 mm, a distance of 1 mm means that there is a water sample between 1. Omm and 1.5 mm from the coil. This distance corresponds to the distance (1.2 mm) between the two semicircular coils of the Doub I e _D type coil. From this result, the Doub Ie_D type coil can measure the position (depth) separated by about the gap of the half-moon shaped coil, and can measure a little inside of the sample.
  • the Doub I e _D type coil matches the geometric dimensions of the coil. It can be seen that the measurement depth changes. Therefore, it is possible to measure the thickness direction (depth direction) distribution in the polymer film by using a coil that matches the desired measurement depth.
  • PEM polymer electrolyte membrane
  • Flemion registered trademark manufactured by Asahi Glass Co., Ltd.
  • the dimension of PEM is 15mmX 15mmX thickness 0.5mm.
  • the membrane was standardized by soaking in advance for 3 hours each in the order of 80 ° C 3% hydrogen peroxide, ion exchange water, 1 N hydrochloric acid, and ion exchange water.
  • the water content of PEM was calculated from the increase in mass by measuring the mass of PEM fully dried using an electronic balance and measuring the mass of PEM in the water-containing state.
  • the water content of P EM 1 4. 9 - was performed by changing [H 2 0 / S0 3 H +] and 1 2. 4 [H 2 0 / S0 3 -H +] and.
  • the PEM sample itself is the same sample, and only the water content is different.
  • N MR measurement parameters were as follows.
  • the 90-degree excitation pulse repetition time (TR) is 5 seconds
  • the 90-degree excitation pulse dummy count is 0
  • the NMR signal integration count is 64
  • the resonance frequency is 13.07 MHz.
  • the temperature of the polymer electrolyte membrane (PEM) was about 25 ° C.
  • PEM polymer electrolyte membrane
  • FIG. 15 shows the calculated T 2 (CPMG) value by performing C PMG measurement three times with PEM of each water content. The straight line is based on the average of three T 2 (CPMG) values.
  • Figure 16 shows the relationship between echo signal intensity and water content obtained from two water content PEMs.
  • the echo signal strength used here is the average of the third, fourth, and sixth echo signal strengths obtained by CPMG measurement. This averaging operation was performed in order to suppress variations in signal intensity.
  • T 2 (CPMG) value acquisition experiments were conducted using an electrode-catalyzed polymer electrolyte membrane (MEA) with an electrode and catalyst applied to the surface of the polymer electrolyte membrane (PEM).
  • MEA electrode-catalyzed polymer electrolyte membrane
  • PEM polymer electrolyte membrane
  • ME A was conducted with reference to Non-Patent Document 2. Specifically, a polymer electrolyte membrane manufactured by Asahi Glass Co., Ltd. was prepared by electrolessly plating Pt and Ir on the anode side and Pt on the cathode side. The dimensions of 1 ⁇ 1 ⁇ 8 are 17 mm x 15 mm square, 500; Um thickness
  • the standardized MEA was lifted from the ion-exchanged water just before the experiment. The water was wiped off by pressing against the tip. The water content of MEA just before the experiment is about 15 [H 2 0 / S0 3 -H +]. After wiping off the water, the MEA was quickly sandwiched between two cover glasses (dimensions 18 mm x 18 mm, thickness 0.1 2 mm) and sealed with a polyimide film to prevent drying.
  • the MEA was placed at the position shown in FIG. A Doub I e-D type coil was placed on a permanent magnet with a gas flow path, and an “electrode / catalyst polymer electrolyte membrane (MEA)” was placed on it. This was placed in a brass shield box and CP MG measurement was performed to obtain an echo signal.
  • N MR measurement parameters were as follows.
  • the 90-degree excitation pulse repetition time (TR) is 5 seconds
  • the 90-degree excitation pulse dummy count is 0
  • the NMR signal integration count is 64
  • the resonance frequency is 13.07 MHz.
  • Electrode ⁇ The temperature of the polymer electrolyte membrane with catalyst (MEA) was about 25 ° C.
  • CPMG measurement of a polymer electrolyte membrane (ME A) with electrode and catalyst can be performed and calculated. It can also be seen that the water content in the polymer electrolyte membrane can be estimated from the T 2 (CPMG) value.
  • Non-Patent Document 1 describes that the water content value of the solid polymer electrolyte membrane of the fuel cell is about 4 to 6 [H 2 0 / S0 3 -H +]. , And for example, if a change in water content of about 2 [H 2 0 / S0 3 ⁇ H +] can be detected, it can be suitably used for evaluation of a solid polymer electrolyte membrane of a fuel cell. In this respect, it can be seen from the above measurement results that the method of this example has a detection sensitivity that can sufficiently detect fluctuations in the water content of the solid polymer membrane.
  • the concentration per unit volume of the proton solvent in the fuel gas and the oxidant gas flowing in the separator flow channel during the operation of the fuel cell is equal to the concentration of the proton solvent in the polymer electrolyte membrane.
  • the echo signal from the gas is negligibly small. For this reason, even if a gas containing a protonic solvent is allowed to flow through the flow channel groove of the permanent magnet, T 2 (C PMG) measurement can be performed with the same measurement accuracy as when the gas is not flowed.
  • the excitation magnetic field distribution ⁇ ⁇ created by the Double-D type coil is theoretically analyzed, and the echo signal intensity distribution received by the coil when using the CPMG method S SE , Detect (equivalent to the measurement region) was calculated quantitatively.
  • the distance L between the two D-shaped coils was changed, it was confirmed that the NMR signal acquisition region was separated from the coil. It was also shown that the measurement depth can be changed by adjusting the interval L.
  • FIGS. 18 (a) and 18 (b) are diagrams showing the configuration of the Doub I e-D type coil analyzed in this example.
  • Fig. 18 (a) shows the shape of the Double-D coil in the case of one turn. However, in actual calculations, as shown in Fig. 18 (b), three turns are used. did.
  • the distance L between two D-shaped coils was changed to 0.6 mm, 1.2 mm, 1.8 mm and 2.4 mm, and the NMR signal acquisition area (measurement area) received by the coil I examined the changes.
  • FIGS. 20 (a) and 20 (b) the circular coil shown in FIGS. 20 (a) and 20 (b) will be described as an example.
  • the planar shape of the coil is circular, but in the analysis, it is the shape shown in FIG. 18 (b).
  • Line integration is performed over the entire circumference of the coil.
  • the magnetic field generated at point ⁇ is obtained by moving point Q on the coil along the coil and integrating the magnetic field created at each point Q over the entire circumference of the coil (obtaining the sum).
  • the arc of the Double-D coil was divided into a number of sections and approximated as being represented by a straight line of length c L – d s [m] within the section. It is assumed that t in that interval changes smoothly with increasing angle 0.
  • the straight part of the coil was divided as a straight element. This makes it possible to calculate Equation (2) numerically.
  • one D-type coil on one side was divided into 16 straight lines, and the curved portion was also divided into 16 straight lines. This division method was the same for the first roll, the second roll, and the third roll (innermost).
  • Figure 21 shows the parameters when dividing.
  • Figure 18 (b) shows the overall shape of the divided elements with dots.
  • FIG. 23 is a diagram showing the overall contour lines of a 3-turn Double-D coil.
  • FIG. 24 shows the z-position distribution H x (z p ) of the magnetic field strength in the X direction.
  • FIG. 26 and FIG. 27 are enlarged views of only the straight conducting wire portion (FIG. 25) of FIG. 23 and FIG. 24, respectively.
  • Figure 23 and In Fig. 26, the cross section of the coil is indicated by a white circle ( ⁇ ).
  • a magnetic field that can be considered uniform is formed around the apex where the magnetic field strength is highest.
  • this region is the measurement region for the Double_D type coil, variations in the excitation oscillating magnetic field can be suppressed, and more accurate measurement can be performed. It can be seen that the measurement area should be about 0.6 to 0.7 mm away from the coil.
  • the same magnetic field analysis was performed by changing the distance L between the two D-shaped coils to 0.6 mm, 1.2 mm, 1.8 mm, and 2.4 mm.
  • the shape of the analysis model with the interval L of 1.2 mm corresponds to Fig. 18 (b).
  • the diameter (D-3) is also the same as the model shape shown in Fig. 18 (b).
  • the number of element divisions for the straight line and the arc is the same. Therefore, as the interval L was increased, the straight line portions of each coil were separated from each other in the soil Y direction, the center angle of the arc portion was reduced, and the analysis points were re-probed.
  • the X-direction magnetic field strength distribution H x (x p , y p , 2 of the 3-turn Double-D coil when the distance L between the two D-type coils is 2.4 mm is shown in Fig.
  • Fig. 29 shows the z-position distribution H x (z p ) of the magnetic field strength in the X direction when L is 2.4 mm.
  • Figure 30 shows the z-position distribution H x (0, 0, z p ) of the magnetic field strength in the X direction when the distance L between the linear conductors of the two D-type coils of the Double-D type coil is changed.
  • the signal reception sensitivity of the Double-D coil is based on the magnetic field H x (x p , y p , z
  • S SE illustrates Detect (x p, y p, z p) a.
  • the X z plane of only the central region of the Double-D coil is shown enlarged.
  • the cross section of the three straight line conductors of the Doubl eD type coil is shown schematically. The typical meaning is that the wire diameter is analyzed as zero.
  • a region where the signal intensity is approximately 0.8 or more is shown surrounded by a dotted line.
  • the echo signal is mainly acquired by the Double-D type coil, and this area can be regarded as the measurement area of the Double_D type coil in this case.
  • Figure 32 shows the echo signal received intensity distribution on the z-axis in Figure 31 S SE , Detect (0, 0, z p FIG.
  • the region where the signal intensity is approximately 0.8 or more as shown by the arrow is regarded as the measurement region with the Double-D coil, it is the same as the region surrounded by the dotted line in Fig. 31. Become.
  • reception intensity distribution S SE, Detect (X p, y p, Z p) is a diagram showing a. In FIG. 33, as in FIG. 31, the X z plane of only the central region of the Double-D coil is shown enlarged.
  • Fig. 33 the region where the signal intensity is approximately 0.8 or more is shown surrounded by a dotted line.
  • the region where the signal strength is approximately 0.8 or more is widened, and at the same time, the region moves away from the coil.
  • Fig. 34 shows the echo signal reception intensity distribution on the Z-axis in Fig. 33 S SE , Detect (0,
  • Fig. 34 the range that can be regarded as the measurement area of the Double-D coil is indicated by arrows. Also in Fig. 34, compared to Fig. 32, it can be seen that the measurement area expands and at the same time moves away from the coil.
  • Figure 35 shows the echo signal reception intensity distribution S SE on the z axis when the distance L between the two D-shaped coils is changed to 0.6 mm, 1.2 mm, 1.8 mm, and 2.4 mm.
  • det eot is a diagram showing a (0, 0, Z p) .
  • Example 2 a three-turn coil was analyzed, but it was used in Example 1.
  • the width of the coil bundle is almost the same as that of the coil used in this example. If this width is about the same, it can be considered that a magnetic field similar to that of the 5-turn coil used in Example 1 is formed.

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Abstract

La présente invention concerne un dispositif de mesure (100) assurant la mesure locale de la quantité de solvant protique au niveau d'une zone spécifique dans une membrane (115) par le procédé de résonance magnétique nucléaire. Le dispositif de mesure (100) comporte un aimant permanent (113) pour appliquer un champ magnétostatique à la membrane (115), une bobine plate (114) pour appliquer un champ oscillant d'excitation à une partie de la membrane (115)et des signaux d'acquisition d'écho correspondant au champ oscillant d'excitation, et une section de calcul de quantité de solvant (124) pour calculer la constante de temps de relaxation T2 à partir des intensités des signaux d'écho et pour calculer la quantité de solvant protique dans une zone spécifique de la membrane (115) à partir de la constante de temps de relaxation T2 calculée. Une fente de passage à travers laquelle un fluide contenant le solvant protique circule est formée dans l'aimant permanent (113). La membrane (115) est formée parallèle à la surface de formation de passage de l'aimant permanent (113), et l'aimant permanent (113) applique un champ magnétostatique dans la direction de l'épaisseur de la membrane (115).
PCT/JP2007/001283 2006-11-22 2007-11-21 Dispositif de mesure, pile à combustible comportant un tel dispositif, et procédé de mesure WO2008062561A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010003628A (ja) * 2008-06-23 2010-01-07 Keio Gijuku 燃料電池用測定装置および燃料電池システム

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JP2004170297A (ja) * 2002-11-21 2004-06-17 Rikogaku Shinkokai 導電性部材間の水分分布測定方法、高分子膜の水分分布測定セル及び高分子膜の水分分布測定装置
WO2006030743A1 (fr) * 2004-09-13 2006-03-23 Keio University Procédé et appareil pour mesurer localement la quantité de solvant protonique dans un spécimen

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JP2004170297A (ja) * 2002-11-21 2004-06-17 Rikogaku Shinkokai 導電性部材間の水分分布測定方法、高分子膜の水分分布測定セル及び高分子膜の水分分布測定装置
WO2006030743A1 (fr) * 2004-09-13 2006-03-23 Keio University Procédé et appareil pour mesurer localement la quantité de solvant protonique dans un spécimen

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010003628A (ja) * 2008-06-23 2010-01-07 Keio Gijuku 燃料電池用測定装置および燃料電池システム

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