WO2011155669A1 - Capteur spr pour mesure de combustible d'une pile à combustible ayant une surface en couche mince métallique modifiée, et procédé de fabrication associé - Google Patents

Capteur spr pour mesure de combustible d'une pile à combustible ayant une surface en couche mince métallique modifiée, et procédé de fabrication associé Download PDF

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Publication number
WO2011155669A1
WO2011155669A1 PCT/KR2010/006949 KR2010006949W WO2011155669A1 WO 2011155669 A1 WO2011155669 A1 WO 2011155669A1 KR 2010006949 W KR2010006949 W KR 2010006949W WO 2011155669 A1 WO2011155669 A1 WO 2011155669A1
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WIPO (PCT)
Prior art keywords
spr sensor
fuel
thin film
fuel cell
concentration
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PCT/KR2010/006949
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English (en)
Korean (ko)
Inventor
이혜진
심혜림
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경북대학교 산학협력단
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Publication of WO2011155669A1 publication Critical patent/WO2011155669A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • G01N21/553—Attenuated total reflection and using surface plasmons
    • 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
    • H01M8/0444—Concentration; Density
    • H01M8/04447—Concentration; Density of anode reactants at the inlet or inside the fuel cell
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N2021/258—Surface plasmon spectroscopy, e.g. micro- or nanoparticles in suspension
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an SPR sensor for measuring fuel having a modified metal thin film surface and a method of manufacturing the same.
  • a fuel cell is a battery that directly converts chemical energy generated by oxidation of a fuel into electrical energy.
  • the fuel cell is characterized in that the reactants are continuously supplied from the outside and the reaction products are continuously removed out of the system.
  • Fuels mainly used in fuel cells include methanol, ethanol and formic acid. As fuel is consumed to generate electricity, continuous injection of fuel is essential. Accordingly, a system capable of real-time detection of fuel concentration is required for efficient utilization of fuel cells.
  • the SPR sensor refers to a sensor for measuring the concentration of a substance by Surface Plasmon Resonance (SPR), and has a characteristic of sensitively measuring the concentration of a fluid substance in contact with the surface of the sensor.
  • SPR Surface Plasmon Resonance
  • a gold thin film is generally used as the SPR sensor. When fuel comes into contact with the surface of the gold thin film, the concentration of the signal varies depending on the concentration, and thus the concentration of the fuel can be measured.
  • the SPR sensor if the fuel concentration is measured by the SPR sensor, the signal becomes unstable and its sensitivity is low. This is because the surface of the gold thin film is hydrophobic, whereas the fuel of the fuel cell is mostly hydrophilic, and thus the interaction at the interface is not smooth. Accordingly, there is a limit in measuring accurate fuel concentration due to bubble generation and signal instability on the surface of the gold thin film.
  • the present inventors while studying the surface treatment, which is the key in developing the fuel cell SPR sensor for efficient operation of the fuel cell system, by chemical treatment on the surface of the conventional gold thin film chip as a fuel cell sensor Confirmed that the usability of the can be improved and completed the present invention.
  • the present invention is to provide an SPR sensor for measuring the fuel concentration of the fuel cell that can not only accurately measure the fuel concentration of the fuel cell accurately and reproducibly, but also can be applied to an existing SPR sensor.
  • the present invention is to provide a method for manufacturing an SPR sensor for measuring the fuel concentration of the fuel cell that can improve the characteristics of the SPR sensor without undue increase of complex process and process cost.
  • the present invention is a SPR sensor for measuring the fuel concentration of the fuel cell, the SPR sensor comprises a gold thin film chip, the surface of the gold thin film chip is modified with a polymer having a hydrophilic group It provides an SPR sensor characterized in that.
  • SPR sensor used in the present invention means a sensor for measuring the concentration of a substance and the like by Surface Plasmon Resonance (SPR).
  • SPR Surface Plasmon Resonance
  • the SPR method can measure the interactions between molecules using optical principles without a separate label such as a fluorescent material.
  • Surface plasmons are quantized vibrations of free electrons that propagate along a conductor surface, such as a metal surface. These surface plasmons pass through a dielectric medium such as a prism and enter the metal film at an angle above the critical angle of the dielectric medium. It is excited by incident light and causes resonance at a certain angle. The angle of incidence, ie resonance angle, at which this resonance occurs is sensitive to the change in refractive index of the material in proximity to the thin metal film. Using this property, the SPR sensor can quantitatively analyze a sample from a change in refractive index of a material, that is, a sample close to a metal thin film, and apply the same to measure a fuel concentration of a fuel cell
  • Gold thin film In order to measure the fuel concentration of a fuel cell among the SPR sensors, a gold thin film is generally used.
  • Gold thin film has the advantage that it can be used stably because it does not cause additional chemical reactions such as fuel of a fuel cell such as methanol or ethanol.
  • the surface of the gold thin film is hydrophobic, the signal change is irregular due to problems such as surface tension or problems caused by a change in the interface generated when the fuel cell of the hydrophilic fuel cell contacts the surface of the gold thin film.
  • the present invention is to modify the surface of the gold thin film with a polymer having a hydrophilic group, thereby making the surface of the gold thin film hydrophilic to solve the above problems, it is possible to improve the accuracy and reproducibility of the SPR sensor.
  • the polymer having a hydrophilic group means a compound in which one end of the polymer has a reactor capable of bonding with a gold thin film, and the other end has a hydrophilic reactor.
  • 11-mercapto-undecylamine, 11-mercapto-undecanoic acid, 11-mercapto-undecanoic acid, 11-mercapto-1-undecanol (11- mercapto-1-undecanol), or poly-ethylene-glycol may be used.
  • the accuracy and reproducibility of the SPR sensor is increased, and in particular, the concentration of methanol, ethanol or formic acid can be measured very accurately. Can be.
  • step 1 the step of dissolving a polymer having a hydrophilic group in a solvent
  • step 2 Method of manufacturing an SPR sensor for measuring the fuel concentration of the fuel cell comprising the step of immersing the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell in a solution in which the polymer having the hydrophilic group dissolved (step 2) To provide.
  • Step 1 is a step of dissolving a polymer having a hydrophilic group in a solvent, the polymer means a compound having one end of the polymer can be combined with a gold thin film, the other end having a hydrophilic reactor.
  • the polymer means a compound having one end of the polymer can be combined with a gold thin film, the other end having a hydrophilic reactor.
  • 11-mercapto-undecylamine, 11-mercapto-undecanoic acid, 11-mercapto-undecanoic acid, 11-mercapto-1-undecanol (11- mercapto-1-undecanol), or poly-ethylene-glycol may be used.
  • methanol may be preferably used, but is not limited thereto.
  • Step 2 is a step for modifying a polymer having a hydrophilic group on the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell, the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell
  • the surface of the gold thin film may be modified by immersion in a solution in which a polymer having a group is dissolved. Immersion time is preferably 11 to 13 hours, so that the polymer can be sufficiently modified.
  • the SPR sensor and its manufacturing method for measuring the fuel concentration of the fuel cell according to the present invention has the following features.
  • the SPR sensor for measuring the fuel concentration of the fuel cell according to the present invention can measure the fuel concentration of the fuel cell accurately and reproducibly.
  • the fuel cell is operated for a long time according to the supply of fuel, and it is important to accurately measure the concentration of the fuel during the long time of operation.
  • the SPR sensor for measuring the fuel concentration of a commonly used fuel cell uses a gold thin film chip, it is difficult to accurately measure the concentration due to the hydrophobicity of the surface of the gold thin film chip and the hydrophilicity of the fuel.
  • the SPR sensor for measuring the fuel concentration of the fuel cell according to the present invention can be applied as it is to the SPR sensor used in the past.
  • the SPR sensor can be used as it is, and a simple method can increase the accuracy of the SPR sensor. Accordingly, it is possible to effectively improve the characteristics of a conventionally used fuel cell.
  • the manufacturing method of the SPR sensor for measuring the fuel concentration of the fuel cell according to the present invention can be manufactured by a simple method of immersing the SPR sensor in a solution in which a hydrophilic polymer is dissolved. Accordingly, it is possible to improve the characteristics of the conventional SPR sensor used in a simple manner, it is possible to improve the characteristics of the SPR sensor without undue increase of complex process and process cost.
  • Figure 1 shows the signal change of the SPR sensor when injecting methanol.
  • Figure 2 shows the signal change of the SPR sensor when ethanol is injected.
  • Figure 3 shows the signal change of the SPR sensor when injecting formic acid.
  • Figure 4 shows the signal change of the SPR sensor according to the change in the concentration of formic acid.
  • Figure 5 shows the signal change of the SPR sensor according to the change in the concentration of formic acid.
  • FIG. 6 shows a calibration curve according to an embodiment of the present invention.
  • FIG. 7 illustrates a result of measuring an RU value for each time zone according to an embodiment of the present invention.
  • 11-mercapto-undecylamine (Dojindo), 11-mercapto-undecanoic acid (Aldrich), 11-mercapto-1-unde in ethanol Canol (11-mercapto-1-undecanol, Aldrich), and poly-ethylene-glycol (SH-poly-ethylene-glycol, Paraon), each of which was modified at a thiol group, were dissolved at a concentration of 1 mM.
  • a gold thin film chip (gold thin film chip manufactured by Kmac (gold thin film chip for microSPR) manufactured by Kmac) was used; BK7 glass substrate (1 cm width ⁇ 1 cm length ⁇ 0.5 cm Thin chromium thin film (approximately 1 nm) and then immersed a 45 nm gold thin film chip) to form a self-assembled monolayer to modify the surface of the gold thin film with a polymer. Immersion time was adjusted to 12 hours.
  • the gold thin film chip of the SPR sensor (using Kmac's microSPR equipment) whose surface was modified with MUAM showed the most sensitive signal change.
  • the gold thin film chip of the SPR sensor whose surface was modified with MUD when formic acid was injected showed the most sensitive signal change.
  • the signal change was shown quantitatively according to the concentration of formic acid, and in particular, since the exact signal change was reproducible according to each concentration, the Refractive Unit (RU) value corresponding to each concentration was changed. It could be confirmed that almost identical.
  • RU Refractive Unit
  • the SPR sensor for measuring the fuel concentration of a fuel cell is required for long-term sustainability at the same time as sensitive response.
  • the formic acid was maintained at a concentration of 2.5M, and the RU value was measured at each time zone, and the results are shown in FIG. 7.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Sustainable Energy (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Sustainable Development (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Fuel Cell (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

La présente invention concerne un capteur à résonance de plasmons de surface (SPR) pour la mesure de la concentration en combustible d'une pile à combustible, qui peut mesurer de manière exacte et reproductible la concentration en combustible d'une pile à combustible et être appliqué à des capteurs SPR existants. La présente invention concerne également un procédé de fabrication du capteur SPR pour la mesure de la concentration en combustible d'une pile à combustible, qui peut augmenter les propriétés du capteur SPR sans augmentations excessives de processus compliqués et de coûts de fabrication.
PCT/KR2010/006949 2010-06-10 2010-10-11 Capteur spr pour mesure de combustible d'une pile à combustible ayant une surface en couche mince métallique modifiée, et procédé de fabrication associé WO2011155669A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020100055051A KR101706384B1 (ko) 2010-06-10 2010-06-10 금속 박막 표면이 개질된 연료전지의 연료측정용 ｓｐｒ 센서 및 이의 제조방법
KR10-2010-0055051 2010-06-10

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WO2011155669A1 true WO2011155669A1 (fr) 2011-12-15

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030017579A1 (en) * 2001-07-10 2003-01-23 Corn Robert M. Surface plasmon resonance imaging of micro-arrays
US20030100127A1 (en) * 2001-07-10 2003-05-29 Corn Robert M. Fusion protein arrays on metal substrates for surface plasmon resonance imaging
JP2009042210A (ja) * 2007-07-13 2009-02-26 Fujifilm Corp 表面プラズモン共鳴測定用チップ
KR20100041565A (ko) * 2008-10-14 2010-04-22 강릉원주대학교산학협력단 기능성 작용기를 물질의 표면에 도입하는 방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002122600A (ja) * 2000-10-12 2002-04-26 Nippon Laser & Electronics Lab バイオセンサー用センサーチップ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030017579A1 (en) * 2001-07-10 2003-01-23 Corn Robert M. Surface plasmon resonance imaging of micro-arrays
US20030100127A1 (en) * 2001-07-10 2003-05-29 Corn Robert M. Fusion protein arrays on metal substrates for surface plasmon resonance imaging
JP2009042210A (ja) * 2007-07-13 2009-02-26 Fujifilm Corp 表面プラズモン共鳴測定用チップ
KR20100041565A (ko) * 2008-10-14 2010-04-22 강릉원주대학교산학협력단 기능성 작용기를 물질의 표면에 도입하는 방법

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KR20110135249A (ko) 2011-12-16
KR101706384B1 (ko) 2017-02-13

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