JP2021183946A - Spectrometer, analysis system, and analysis method - Google Patents

Abstract

To easily adjust phase matching conditions for generating CARS light.SOLUTION: A spectrometer (30) irradiates a sample with a first laser beam and a second laser beam having different angular frequencies from each other and detects intensity of coherent anti-Stokes Raman scattering light generated from the sample. The spectrometer (30) includes an optical splitter (37) that splits a second laser beam into two or more laser beams; a plurality of converters (34) that convert characteristics of the two or more second laser beams into characteristics different from each other; and a switching section (39) that selects one of the two or more converted second laser beams and switches the second laser beams with which the sample is irradiated together with the first laser beam.SELECTED DRAWING: Figure 5

Description

The present invention relates to a spectrometer, an analytical system and an analytical method.

Spectroscopy is widely used for qualitative or quantitative analysis of samples. For example, one of the spectroscopic methods, the Coherent Anti-Stokes Raman Scattering (CARS) method, is used for measuring the water content in a fuel cell (see Patent Document 1). Spectroscopy is non-destructive and non-contact measurable and is particularly useful for product evaluation.

Japanese Unexamined Patent Publication No. 2016-156813

To analyze the vibrational modes of the various molecules in the sample, the CARS method irradiates the sample with two laser beams with different angular frequencies ω1 and ω2 (ω1> ω2). When the difference between the frequencies of the two lights (ω1-ω2) and the vibration mode of the molecules in the sample match, the coherent anti-Stoke Raman scattered light (hereinafter also referred to as CARS light) having an angular frequency of 2ω2-ω1 from the sample. .) Occurs.

The intensity of the CARS light varies not only with the relative amount of the vibration source in the sample but also with the phase matching condition with the irradiated laser light. Therefore, it is possible to increase the detection intensity of CARS light by adjusting the characteristics such as the polarization direction and frequency of the laser light. However, in order to adjust the characteristics, it was necessary to modify the system, such as replacing an optical converter such as a photonic crystal fiber, and it was necessary to interrupt the analysis operation each time the adjustment was made.

An object of the present invention is to easily adjust the phase matching conditions for generating CARS light.

The spectroscope (30) of one aspect of the present invention irradiates a sample with first laser light and second laser light having different angular frequencies, and detects the intensity of coherent anti-Stokes slamman scattered light generated from the sample. A total (30), an optical branching device (37) that branches the second laser beam into two or more, and a plurality of converters (34) that convert the characteristics of the two or more second laser beams into different characteristics. ), And a switching unit (39) for selecting one of the two or more converted second laser beams and switching the second laser beam to irradiate the sample together with the first laser beam.

The analysis system (100) of another aspect of the present invention is based on a spectrometer (30) that irradiates a sample with laser light and measures the intensity of the light generated from the sample, and the measured light intensity. A diagnostic device (50) for analyzing the sample is provided, and the spectrometer (30) includes an optical branching device (37) for branching the second laser beam into two or more, and the second or higher second laser beam. Select a plurality of converters (34) that convert the characteristics of the two laser lights into different characteristics, and one of the two or more converted second laser lights, and irradiate the sample together with the first laser light. A switching unit (39) for switching the second laser beam is provided.

Another analysis method of the present invention is an analysis method in which a sample is irradiated with first laser light and second laser light having different angular frequencies, and the intensity of coherent anti-Stokes slamman scattered light generated from the sample is detected. The step of branching the second laser beam into two or more, the step of converting the characteristics of the two or more second laser beams into different characteristics, and the step of converting the converted second laser light into two or more. It comprises the step of selecting one and switching the second laser beam to irradiate the sample with the first laser beam.

According to the present invention, the phase matching condition for generating CARS light can be easily adjusted.

It is a schematic diagram which shows the structural example of the analysis system of this embodiment. It is a perspective view of a fuel cell. It is sectional drawing which shows the structure of a cell. It is a schematic diagram which shows the structural example of a CARS spectroscope. It is a schematic diagram which shows the structural example of the CARS spectrometer which can easily adjust the phase matching condition. It is a graph which shows an example of the profile which shows the correlation between the output voltage of a fuel cell, and the intensity of the light derived from water in an electrolyte membrane.

Hereinafter, embodiments of the spectrometer, analysis system, and analysis method of the present invention will be described with reference to the drawings. The configuration described below is an example (representative example) of the present invention, and is not limited to this configuration.

In the following embodiment, an example of analyzing a fuel cell mounted on a vehicle and supplying the driving power of the vehicle will be described. However, in addition to the power supply by the vehicle, a power generation system of another mobile body such as a train, or stationary. The present invention can also be applied to a fuel cell such as a power generation system.

FIG. 1 shows a configuration example of the analysis system 100 according to the embodiment of the present invention.
As shown in FIG. 1, the analysis system 100 includes a spectrometer 30 and a diagnostic device 50. The analysis system 100 of the present embodiment is mounted on the vehicle 200 together with the fuel cell 10 to be analyzed and the control device 60 thereof.

FIG. 2 is a perspective view of the fuel cell 10.
As shown in FIG. 2, the fuel cell 10 includes a stack 10a and a casing 10b.
The periphery of the stack 10a is covered with the casing 10b and sealed.

The stack 10a is composed of a plurality of plate-shaped cells 11 stacked in a row. The periphery of the cell 11 is covered and sealed with the sealing rubber 12.

FIG. 3 shows a configuration example of the cell 11.
As shown in FIG. 3, the cell 11 includes a membrane electrode assembly (MEA) 3, a pair of separators 4, and a sub-gasket 5. The MEA 3 includes an electrolyte membrane 1 and a pair of electrodes 2. The pair of electrodes 2 and the pair of separators 4 are arranged so as to sandwich the electrolyte membrane 1, and the electrodes 2 and the separator 4 are laminated on both sides of the electrolyte membrane 1, respectively.

The electrolyte membrane 1, the electrode 2, and the separator 4 are laminated in the z direction. The peripheral edge of the electrolyte membrane 1 and the electrode 2 not covered by the separator 4 is covered and sealed with the sealing rubber 12.

In the stack 10a, the plurality of cells 11 are stacked in the same z direction as the stacking direction of the electrolyte membrane 1, the electrode 2, and the separator 4. The x-direction and the y-direction are directions orthogonal to each other in the z-direction in the plane of the cell 11.

The electrolyte membrane 1 is an ion-conducting polymer electrolyte membrane. Examples of the electrolyte membrane 1 include perfluorosulfonic acid polymers such as Nafion (registered trademark) and Aquivion (registered trademark); aromatic polymers such as sulfonated polyether ether ketone (SPEEK) and sulfonated polyimide; polyvinyl sulfonic acid, Examples thereof include aliphatic polymers such as polyvinylphosphoric acid.

The electrolyte membrane 1 may be a composite membrane in which a porous base material 1a is impregnated with a polymer electrolyte from the viewpoint of improving durability. The porous base material 1a is not particularly limited as long as it can support a polyelectrolyte, and a porous, woven fabric-like, non-woven fabric-like, or fibril-like film can be used. The material of the porous base material 1a is not particularly limited, but a polymer electrolyte as described above can be used from the viewpoint of enhancing ionic conductivity. Among them, the fluoropolymers such as polytetrafluoroethylene, polytetrafluoroethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene are excellent in strength and shape stability.

Of the pair of electrodes 2, one of the electrodes 2 is an anode and is also called a fuel electrode. The other electrode 2 is a cathode and is also called an air electrode. As the fuel gas, hydrogen gas is supplied to the anode, and oxygen gas or air containing oxygen gas is supplied to the cathode.

At the anode, hydrogen gas (H ₂ ) is supplied, and a reaction that generates electrons (e ⁻ ) and protons (H ⁺ _{) from the hydrogen gas (H 2) occurs.} The electrons move to the cathode via an external circuit (not shown). This movement of electrons causes an electric current to be generated in the external circuit. Protons move to the cathode via the electrolyte membrane 1.

Oxygen gas (O _{2 ) is supplied to the cathode, and oxygen ions (O 2} ⁻ ) are generated by electrons moving from an external circuit. Oxygen ions combine with protons having moved from the electrolyte membrane 1 (2H ^+), it becomes water _(H 2 O).

The electrode 2 includes a catalyst layer 21. The electrode 2 of the present embodiment further includes a gas diffusion layer 22 in order to improve the diffusivity of the fuel gas.

The catalyst layer 21 promotes the reaction of hydrogen gas and oxygen gas by the catalyst. The catalyst layer 21 includes a catalyst, a carrier that supports the catalyst, and ionomers that coat them.
Examples of the catalyst include metals such as platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), palladium (Pd), cobalt (Co), and tungsten (W), mixtures of these metals, alloys, and the like. Can be mentioned. Among them, platinum, a mixture containing platinum, an alloy and the like are preferable from the viewpoints of catalytic activity, toxicity to carbon monoxide, heat resistance and the like.

Examples of the carrier include conductive metal compounds such as mesoporous carbon and titanium oxide. Mesoporous carbon is preferable from the viewpoint of good dispersibility, large surface area, and small particle growth at high temperature even when the amount of catalyst supported is large.
As the ionomer, a polymer electrolyte having the same ion conductivity as that of the electrolyte membrane 1 can be used.

The gas diffusion layer 22 can uniformly diffuse the supplied fuel gas to the catalyst layer 21. As the gas diffusion layer 22, for example, in addition to a porous fiber sheet such as carbon fiber having conductivity, gas permeability and gas diffusivity, a metal plate such as foamed metal or expanded metal can be used.

The separator 4 is a plate provided with a plurality of ribs 4b on the surface, and is also called a bipolar plate. Each rib 4b provides a recess 4a on the surface of the separator 4. The recess 4a forms a fuel gas flow path between the separator 4 and the MEA3. This flow path is also a drainage channel for water generated by the reaction of fuel gas.

As the material of the separator 4, for example, in addition to carbon, a metal such as stainless steel is used.

The sub-gasket 5 is a film or plate that surrounds the outer peripheral edge of the MEA 3 and functions as a support for the MEA 3. As the material of the sub-gasket 5, a resin having low conductivity can be used. The resin material is not particularly limited, and examples thereof include polyphenylene sulfide (PPS), polypropylene-containing polypropylene (PP-G), polystyrene (PS), silicone resin, and fluororesin.

The sub-gasket 5 seals the inside of the cell 11 by coming into contact with the separator 4 at the outer peripheral edge portion.

(window)
The fuel cell 10 includes windows B1 to B3 leading from the outside of the fuel cell 10 to the inside MEA3. The window B1 is provided on the casing 10b, and the window B2 is provided on the sealing rubber 12. The window B3 is provided on the separator 4, the gas diffusion layer 22, and the catalyst layer 21.

The windows B1 and B2 may be opened in any of the x-direction, y-direction, and z-direction. The window B3 opens in the z direction and leads to the window B1 which also opens in the z direction.
The windows B1 to B3 may be merely openings, but from the viewpoint of sealing, they may be glass plates or openings provided with a plate made of a material other than glass that allows light to pass through.

The spectrometer 30 irradiates the MEA3 inside the fuel cell 10 with laser light from the peripheral portion side where the separator 4 is not arranged or from the separator 4 side through these windows B1 to B3, and from the MEA3. It can receive light. The optical path between the spectrometer 30 and the MEA3 may be formed by an optical system such as a mirror, an optical fiber, a waveguide, or the like.

(Spectroscope)
The spectrometer 30 irradiates the sample with light for measurement, for example, laser light. The spectrometer 30 receives light such as reflected light, scattered light, and emitted light generated from the sample by irradiation with laser light, and measures the intensity of the light.

Examples of the spectroscope of the spectrometer 30 include Coherent Anti-Stokes Raman Scattering (CARS), Raman spectroscopy, Infrared Spectroscopy (IR), and FT-IR (Fourier Transform Infrared). Spectroscopy) method and the like.

Among them, the spectrometer 30 is preferably a CARS spectrometer that measures by the CARS method. CARS spectroscopes have higher time resolution than other spectroscopic analysis methods such as Raman spectroscopy. For example, the time resolution of a neutron detector requires 10 seconds or more for detection, but the CARS spectrometer can detect it in less than 1 second, and it becomes possible to analyze the internal state of the fuel cell 10 in real time.

The CARS spectrometer irradiates a sample with two laser beams having different angular frequencies, and measures the intensity of coherent anti-Stoke Raman scattered light (hereinafter, also referred to as CARS light) generated from the sample.

FIG. 4 shows a configuration example of the CARS spectrometer 30A.
As shown in FIG. 4, the CARS spectrometer 30A includes a light source 31, an optical turnout 32, converters 33 and 34, a delay circuit 35, a detector 36 and a probe 38. The optical path in the CARS spectrometer 30A is formed by an optical system such as a mirror (not shown), but may be formed by an optical fiber, a waveguide, or the like.

In the CARS spectrometer 30A, the laser light emitted from the light source 31 is branched into two laser lights by the optical turnout 32. Examples of the light source 31 include a titanium sapphire laser, a pulse laser light source, and the like. Examples of the optical turnout 32 include an optical system such as a dichroic mirror and a half mirror, a waveguide having a branch, an optical fiber, and the like.

One of the branched laser lights (first laser light) is converted into Stokes light L2, which is laser light having an angular frequency ω2, by the converter 33. Examples of the converter 33 include a photonic crystal fiber, an optical parametric oscillator, and the like. The Stokes light L2 may be white light including light having different wavelengths. By using the Stokes light L2 in a wide wavelength range, various vibration modes can be widely detected.

The other branched laser light (second laser light) is converted into pump light L1 which is laser light having an angular frequency ω1 by the converter 34. Examples of the converter 34 include a photonic crystal fiber, an optical parametric oscillator, and the like. The angular frequency ω1 of the pump light L1 is higher than the angular frequency ω2 of the Stokes light L2. The pump light L1 is guided to the same optical path as the Stokes light L2 via the delay circuit 35.

The converters 33 and 34 can convert not only the angular frequency of the laser light but also the characteristics such as the wavelength of the laser light and the direction of deflection.

The Stokes light L2 and the pump light L1 are focused by the probe 38 and irradiated to the sample S. Since the pump light L1 passes through the delay circuit 35, the sample S is irradiated with a delay from the Stokes light L2. When the difference in angular frequency (ω1-ω2) between the pump light L1 and the Stokes light L2 matches the vibration mode peculiar to the substance in the sample S, the dipole moment of the molecule is resonantly induced and the angular frequency is 2ω1-. CARS light L3 of ω2 is generated.

The detector 36 detects the intensity of the CARS light L3 generated from the sample S. The detector 36 is composed of a photoelectric conversion element such as a spectroscope, a CCD (Charge Coupled Device), and an ICDD (Intensified CCD), but is not limited to these as long as the intensity of light of each wavelength can be measured.

When irradiating the laser beam from the separator 4 side through the windows B1 and B3, the focal position of the laser beam of the spectrometer 30 is changed in the x direction and the y direction (in-plane direction), or the z direction (thickness). By changing to (direction), the position in the x, y, or z direction of irradiating the laser beam can be changed. Further, when irradiating the laser beam from the peripheral edge side of the separator 4 through the windows B1 and B2, the position or the posture of the probe 38 can be changed to change the position in the in-plane direction to irradiate the laser beam. By changing the irradiation position, the sample S can be switched to the electrolyte membrane 1 or the electrode 2.

(CARS spectrometer with easy adjustment of phase matching conditions)
The intensity of the CARS light L3 varies not only by the relative amount of the vibration source in the sample but also by the phase matching condition of the irradiated laser light. The phase matching condition can be adjusted by characteristics such as the polarization direction and frequency of the laser beam irradiating the sample S.

FIG. 5 shows a configuration example of the CARS spectrometer 30B in which the phase matching condition for generating the CARS optical L3 can be easily adjusted. By using the CARS spectroscope 30B instead of the CARS spectroscope 30A, adjustment for increasing the detection intensity of the CARS light L3 becomes easy.

The CARS spectrometer 30B is the same as the CARS spectrometer 30A except that it irradiates the pump light L1. In FIG. 5, the same components as those of the CARS spectrometer 30A shown in FIG. 4 are designated by the same reference numerals.

The CARS spectrometer 30B switches a plurality of pump lights L11 to L13 having different characteristics to irradiate the sample S. Therefore, the CARS spectrometer 30B includes a plurality of optical branching devices 37 that further branch the laser light branched by the optical branching device 32 into two or more laser lights, and a plurality of optical paths that guide each branched light to the sample S. ..

The CARS spectrometer 30B includes one or more converters 34 and delay circuits 35 on each optical path. The converter 34 converts the wavelength, angular frequency, or direction of deflection of light, similar to the converter 34 in the CARS spectrometer 30A. Each laser beam branched by the optical turnout 37 is converted into a plurality of pump lights L11 to L13 having different characteristics by the converter 34 on each optical path.

Further, the CARS spectrometer 30B includes a switching unit 39 for pump lights L11 to L13. In the present embodiment, the switching unit 39 includes shutters 391-293 arranged in each optical path of the pump lights L11 to L13 and a control unit 394 thereof. The shutters 391-293 open and close the optical path from the pump lights L11 to L13 that have passed through the delay circuit 35 to the sample S. The control unit 394 controls to open one of the shutters 391 to 393 and close the rest according to the user's operation.

As a result, of the pump lights L11 to L13, only the pump light selected according to the adjustment operation of the phase matching condition is applied to the sample S. For example, when the pump light selected by the control unit 394 in response to the operator's adjustment operation is the pump light L11, the control unit 394 opens the shutter 391 and closes the shutters 392 and 393. As a result, only the pump light L11 irradiates the sample S together with the Stokes light L2.

The configuration of the switching unit 39 is not limited to this as long as one of the pump lights L11 to L13 can be selected and switched to the selected pump light. For example, instead of branching the laser light for the pump light by the optical turnout 37, a waveguide for guiding the laser light to any of the optical paths of the pump lights L11 to L13 may be provided as the switching unit 39.

Normally, there is one optical path for Stokes light and one optical path for pump light as in the CARS spectrometer 30A, so it is necessary to modify the system such as replacing the converter 34 of pump light L1 in order to adjust the phase matching conditions. be. Therefore, adjustment during measurement is not easy. In particular, it is difficult to modify the system after mounting it on the vehicle 200.

On the other hand, according to the CARS spectrometer 30B, the characteristics of the pump light emitted together with the Stokes light L2, that is, the phase matching condition can be easily obtained by a simple operation of switching the pump lights L11 to L13 even during measurement. Can be adjusted. For example, the pump lights L11 to L13 can be switched to adjust the phase matching condition when the intensity of the CARS light L3 is maximized.

The CARS spectrometer 30B switches between the three pump lights L11 to L13, but the number of switchable pump lights is not limited to three, and may be two or four or more.
Further, instead of the pump light L1, the Stokes light L2 may be branched into two or more and the characteristics thereof may be different to select either one. The characteristics of both the pump light L1 and the Stokes light L2 may be different.

In the CARS spectrometers 30A and 30B, the Stokes light L2 and the pump light L1 are laser lights branched from one light source 31, but each light source is provided with a light source such as an ultrashort pulse laser device having different frequencies from each other. The Stokes light L2 and the pump light L1 may be generated, respectively. In the case of one light source, the measurement conditions can be the same, and in the case of two light sources, it becomes easy to set the generation conditions of the Stokes light L2 and the pump light L1.

(Diagnostic device)
The diagnostic apparatus 50 performs qualitative analysis or quantitative analysis of the metal in the fuel cell 10 based on the measurement result by the spectrometer 30. As the diagnostic device 50, for example, a CPU, a computer equipped with a memory for storing a program executed by the CPU, a microcomputer, or the like can be used.

The qualitative analysis can be performed by identifying the peak due to the vibration mode between the atoms containing the substance to be analyzed in the spectrum obtained by the spectrometer 30. For example, when the analysis target is platinum, a peak due to the Pt-Pt molecule appears near ^{200 cm -1.}

The method of quantitative analysis is not particularly limited, but the amount of substance can be calculated using, for example, reference data. The reference data is data in which the intensity of light detected by the spectrometer 30 is associated with a known amount of metal. The intensity of light can be determined as the intensity or area of the peak due to the vibrational mode of the molecule containing the metal to be analyzed.

Examples of the analysis target include platinum compounds such as platinum or platinum oxide contained in the electrolyte membrane 1. For example, the diagnostic apparatus 50 acquires the measurement results of the spectrometer 30 at different positions in the thickness direction (z direction) or the in-plane direction (xy plane) of the electrolyte membrane 1, and based on the measurement results, the electrolyte membrane 50. By analyzing the platinum or the platinum compound in 1, it is possible to create a profile of platinum distributed in the thickness direction or the in-plane direction of the electrolyte membrane 1. From such a platinum profile, it is possible to grasp the phenomenon of platinum band formation in which platinum is eluted from the catalyst layer 21 to the electrolyte membrane 1.

The analysis target may be not only the electrolyte membrane 1 but also platinum or a platinum compound in the electrode 2 or the sub-gasket 5. By such an analysis, the amount of platinum eluted from the electrode 2 or the amount of platinum eluted into the sub-gasket 5 can be grasped.

Further, the analysis target may be a metal such as nickel or chromium in the electrolyte membrane 1, the electrode 2, or the sub-gasket 5, or a metal compound. By such an analysis, it is possible to grasp the contamination of metal impurities.

The diagnostic device 50 can create a profile used for controlling the output voltage of the fuel cell 10 based on the platinum profile. For example, the diagnostic apparatus 50 controls the output voltage of the fuel cell 10 so as to suppress the elution of platinum based on the profile showing the correlation between the amount of platinum distributed in the thickness direction or the in-plane direction of the electrolyte membrane 1 and the output voltage. Create a profile to do. Information on the output voltage of the fuel cell 10 can be obtained from the control device 60.

Further, the diagnostic device 50 can also create a profile used for controlling the output voltage of the fuel cell 10 based on the driving information of the vehicle 200 and the profile of the platinum. The driving information of the vehicle 200 is, for example, the amount of depression of the accelerator when the vehicle 200 is traveling, the operation information of the steering wheel, and the like, and can be acquired from the control device 60.

For example, the diagnostic device 50 can specify the amount of depression of the accelerator when the strength of platinum is higher than a certain value, and can be taken out from the fuel cell 10 with respect to the amount of depression of the accelerator so that the strength of platinum does not exceed a certain value. It is possible to create a control profile that defines the upper limit of the output voltage.

Further, the diagnostic device 50 may create a control profile for each traveling mode of the vehicle 200. For example, the fluctuation of the output voltage of the fuel cell 10 is larger on a mountain road having a steeper slope than in an urban area. Therefore, the diagnostic device 50 can create a control profile for the driving mode of the mountain road, which suppresses the increase rate and the upper limit of the output voltage of the fuel cell 10 as compared with the control profile in the driving mode in the urban area. ..

The platinum ionized at the cathode is transported to the electrolyte membrane 1 by the water generated by the chemical reaction at the cathode, and a platinum band is formed. Since the amount of water generated depends on the output voltage, the diagnostic apparatus 50 may create a profile of water contained in the electrolyte membrane 1 or the electrode 2 based on the measurement result by the spectrometer 30. Based on each profile of water and platinum, the diagnostic apparatus 50 can also create a profile used for controlling the output voltage so as to suppress the transport of platinum by water.

FIG. 6 shows an example of a profile showing the correlation between the output voltage of the fuel cell 10 and the intensity K of the light derived from water measured in the thickness direction of the electrolyte membrane 1.
In this profile, the light intensity K measured at regular time intervals is plotted at positions where the thickness direction distance from the cathode side is 0, 5, 10, 15 and 20 μm, respectively.

While the fuel cell 10 is generating electricity with an output voltage of 0.1 A / cm ³ , the change in the intensity K is small, and the farther from the cathode, the smaller the intensity K. However, that is the output voltage at the time T1 when pulled from 0.1 A / cm ³ to 1.0A / cm ^3, raised by the sudden increase in the output voltage intensity K also overall, with water many occur Can be analyzed. The closer to the cathode, the greater the intensity K, and a particularly sharp rise in water is observed in the phase of 0 μm in contact with the cathode.

A sharp increase is observed between time T1 and time T2, and the subsequent change in intensity K is small. If time T1-T2 is 5 seconds, the diagnostic device 50, when raising the output voltage from 0.1 A / cm ³ to 1.0A / cm ³ is per second (1.0-0.1) It is possible to create a stepwise control profile that increases the output voltage by / 5 (A / cm ^3). A control profile that suppresses such a sudden output voltage may be created by PID control. When not only the fuel cell 10 but also a secondary battery or the like is mounted as the power source, the suppressed output voltage of the fuel cell 10 may be supplemented by another power source.

The diagnostic device 50 may create a profile used to control the supply of air at the cathode rather than the output voltage. The platinum ionized at the cathode is transported to the electrolyte membrane 1 by the water generated by the chemical reaction at the cathode. Since the amount of water generated increases as the output voltage of the fuel cell 10 increases, the diagnostic apparatus 50 creates a profile that controls the supply amount of air as a fuel gas according to the output voltage. As a result, water that becomes a carrier of platinum can be discharged by air.

Specifically, when the intensity of platinum is low and the output voltage is low, the diagnostic apparatus 50 determines the amount of air supplied to the cathode by the chemical quantity ratio so that the required output voltage can be obtained. When the intensity of platinum is an output voltage higher than a certain value, the diagnostic apparatus 50 determines that the amount of air supplied is increased more than the amount determined by the stoichiometric ratio.

In order to promote the discharge of water to the gas diffusion layer 22 side and prevent the back diffusion of water to the electrolyte membrane 1 side, a hydrophilic sheet for a gas diffusion layer having a contact angle of less than 90 ° is used as the gas diffusion layer 22. It is preferably used.

(Control device)
The control device 60 controls the output voltage of the fuel cell 10 based on signals from various sensors mounted on the vehicle 200. The control device 60 is, for example, an electronic control unit (ECU) or the like.

The control device 60 can control the output voltage of the fuel cell 10 or the supply of air to the cathode based on the control profile created by the diagnostic device 50.

As described above, according to the present embodiment, the laser light for pump light is branched into two or more, the characteristics of the two or more laser lights are converted into different characteristics, and a plurality of pump lights obtained by this conversion. The sample S is irradiated with one of L11 to L13. The characteristics of the pump light can be easily adjusted by a simple operation of switching the pump light L11 to L13. Even during the measurement operation, it is possible to easily adjust the phase matching condition for generating the CARS optical L3.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments.

For example, in the above embodiment, the analysis system 100 analyzes the fuel cell 10 that is generating electricity on the vehicle 200, but analyzes the fuel cell 10 connected to the experimental load instead of the vehicle 200. May be good.

Further, the sample of the CARS spectrometer 30B described above is not limited to the fuel cell 10, and can be used for various samples such as intracellular biomolecules.

100 ... analysis system, 30 ... spectrometer, 31 ... light source, 33, 34 ... converter, 36 ... detector, 50 ... diagnostic device, 10 ... fuel cell, 1 ... Electrolyte membrane, 2 ... Electrode, 21 ... Catalyst layer, 22 ... Gas diffusion layer, 3 ... MEA, 4 ... Separator, 5 ... Subgasket, B1 to B3 ···window

Claims (7)

A spectrometer (30) for irradiating a sample with first laser light and second laser light having different angular frequencies and detecting the intensity of coherent anti-Stoke Raman scattered light generated from the sample.
An optical turnout (37) that splits the second laser beam into two or more,
A plurality of converters (34) that convert the characteristics of the two or more second laser beams into different characteristics, and
A switching unit (39) for selecting one of the two or more converted second laser beams and switching the second laser beam to irradiate the sample together with the first laser beam is provided.
Spectrometer (30). The angular frequency of the second laser beam is higher than that of the first laser beam.
The spectrometer (30) according to claim 1. The transducer (34) converts the wavelength, angular frequency or direction of deflection of the second laser beam.
The spectrometer (30) according to claim 1 or 2. The first laser beam and the second laser beam are laser beams branched from one light source.
The spectrometer (30) according to any one of claims 1 to 3. A spectrometer (30) that irradiates a sample with laser light and measures the intensity of the light generated from the sample.
A diagnostic device (50) that analyzes the sample based on the measured light intensity is provided.
The spectroscope (30) is
An optical turnout (37) that splits the second laser beam into two or more,
A plurality of converters (34) that convert the characteristics of the two or more second laser beams into different characteristics, and
A switching unit (39) for selecting one of the two or more converted second laser beams and switching the second laser beam to irradiate the sample together with the first laser beam is provided.
Analytical system (100). The sample is an electrolyte membrane (1) provided in the fuel cell (10), or a pair of electrodes (2) arranged on both sides of the electrolyte membrane (1).
The diagnostic apparatus (50) analyzes the metal or water contained in the electrolyte membrane (1) or the electrode (2).
The analysis system (100) according to claim 5. An analysis method in which a sample is irradiated with first laser light and second laser light having different angular frequencies, and the intensity of coherent anti-Stoke Raman scattered light generated from the sample is detected.
The step of branching the second laser beam into two or more,
The step of converting the characteristics of the two or more second laser beams into different characteristics, and
A step of selecting one of the two or more converted second laser beams and switching the second laser beam to irradiate the sample with the first laser beam.
Analytical method.

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