WO2014021208A1 - 高プロトン伝導性ポリマーフィルム、その製造方法及び湿度センサー - Google Patents
高プロトン伝導性ポリマーフィルム、その製造方法及び湿度センサー Download PDFInfo
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- G01N27/28—Electrolytic cell components
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- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
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- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/121—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid for determining moisture content, e.g. humidity, of the fluid
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/37—Metal complexes
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/37—Metal complexes
- C08G2261/374—Metal complexes of Os, Ir, Pt, Ru, Rh, Pd
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/37—Metal complexes
- C08G2261/376—Metal complexes of Fe, Co, Ni
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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Definitions
- the present invention relates to a high proton conductive polymer film, a method for producing the same, and a humidity sensor.
- the high proton conductive polymer film is a polymer film having high proton conductivity.
- a material with high proton conductivity is a material whose current-voltage characteristics fluctuate with high sensitivity to humidity, and the conductivity increases at high humidity.
- Patent Document 1 relates to a coordination polymer metal complex containing copper ions.
- the coordination polymer metal complex containing these copper ions has a high current sensitivity and a high sensitivity to humidity, and the conductivity increases at high humidity. Therefore, these materials are materials having high proton conductivity.
- High proton conductive polymer films are used, for example, as proton exchange membranes for fuel cells and humidity sensors (Patent Documents 1 to 3).
- Nafion As a proton exchange membrane, Nafion (registered trademark) is known. Nafion is a sulfonated tetrafluoroethylene copolymer, and the sulfonic acid group grafted to the end of the polytetrafluoroethylene backbone has a negative charge, so that the positively charged proton group can easily move between them. Thus, proton conductivity is increased.
- Non-Patent Document 9 examines the proton conduction mechanism in the Nafion membrane.
- Nafion was developed in the 1960s and has been blended with various other polymers to improve stability and the like.
- a proton exchange membrane made of Nafion modified to include a hyperbranched polymer has been disclosed as a proton exchange membrane having a conductivity of 8 ⁇ 10 ⁇ 2 Scm ⁇ 1 (Patent Document 1).
- conductivity (25 °C) 2 ⁇ 10 -2 Scm -1 proton exchange membrane, Nafion 112 conductivity (25 °C) 2.7 ⁇ 10 -2 Scm -1 is also disclosed (Patent Document 2) .
- Non-Patent Documents 8, 10, and 11 describe that Nafion is a material with high proton conductivity because the current-voltage characteristics of Nafion fluctuate with high sensitivity to humidity and the conductivity increases at high humidity. Yes. Specifically, it is disclosed that the proton conductivity (30 ° C., two-terminal method) of Nafion 112, 115, 117 is about 0.038 to 0.047 Scm ⁇ 1 (Non-patent Document 8). The conductivity of the proton exchange membrane has also been measured by impedance spectroscopy (Non-patent Document 10). Further, as a result of measuring the impedance of the Nafion film, it is disclosed that the conductivity (room temperature, 100% RH) of the Nafion film is 0.073 Scm ⁇ 1 (Non-patent Document 11).
- a coordination polymer metal complex has been disclosed as having a proton conductivity (100% RH) 10 ⁇ 2 Scm ⁇ 1 comparable to that of Nafion (Patent Document 3).
- Metal-organic frameworks (Metal-organic frameworks: MOFs, also known as porous coordination polymers (PCPs)) have been reported as materials having high proton conductivity (Non-Patent Documents 1-7). These MOFs (PCPs) are also materials having high proton conductivity because the current-voltage characteristics fluctuate with high sensitivity to humidity and the electric power increases at high humidity.
- the proton conductivity (298K, 95% RH) of PCPs described in Non-Patent Document 1 is 2.3 ⁇ 10 ⁇ 9 to 2.0 ⁇ 10 ⁇ 6 Scm ⁇ 1 (see, for example, Table. 1).
- Non-patent Document 14 a humidity sensor using polyaniline to which polyvinyl alcohol (PVA) is added is disclosed (Non-patent Document 14), and the resistance value of this material is measured when the proton conductivity of polyaniline varies greatly with humidity. It can be used as a humidity sensor.
- PVA polyvinyl alcohol
- Japanese Unexamined Patent Publication No. 2004-31173 A) Japanese Unexamined Patent Publication No. 2010-155991 (A) Japanese Unexamined Patent Publication No. 2004-31173 (A)
- the present invention provides a proton conducting membrane having a proton conductivity (room temperature, 95% RH) of 3 ⁇ 10 ⁇ 2 Scm ⁇ 1 or more and usable in a neutral solvent atmosphere, a method for producing the same, and a highly sensitive humidity sensor.
- the task is to do.
- the present inventor has developed a proton conducting membrane comprising an organic / metal hybrid polymer and having a proton conductivity (room temperature, 95% RH) of 0.034 ⁇ 10 ⁇ 4 Scm ⁇ 1 to 1.3 ⁇ 10 ⁇ 1 Scm ⁇ 1. I was able to create it. This material was found to be able to be used in a neutral solvent atmosphere, unlike Nafion, which itself is strongly acidic, and completed the present invention.
- the present invention has the following configuration.
- a film of an organic / metal hybrid polymer comprising one or more metal ions selected from the group of Fe ions, Co ions, Ru ions, Zn ions, and Ni ions and bis (terpyridyl) benzene.
- a high proton conductive polymer film characterized by being.
- M is one or more metal ions selected from the group of Fe ions, Co ions, Ru ions, Zn ions, and Ni ions, and n is an integer of 5 or more and 1000 or less.
- the solvent is water or an organic solvent and a mixture thereof, and the organic solvent is any one selected from the group consisting of alcohol, acetonitrile, dimethyl sulfoxide, and dimethylformamide.
- a substrate two electrodes formed on one surface of the substrate so as to be separated from each other, and a film formed on the one surface so as to cover the two electrodes, wherein the film is (1) Or the humidity sensor characterized by being the high proton conductive polymer film as described in (2).
- the high proton conductive polymer film of the present invention comprises one or more metal ions selected from the group of Fe ions, Co ions, Ru ions, Zn ions, and Ni ions, and bis (terpyridyl) benzene.
- Proton conductivity room temperature, 95% RH is 3 ⁇ 10 ⁇ 2 Scm ⁇ 1 or higher because it is an organic / metal hybrid polymer film, and a proton conductive membrane that can be used in a neutral solvent atmosphere is provided. Can do.
- the method for producing a highly proton conductive polymer film of the present invention includes one or more metal ions selected from the group of Fe ions, Co ions, Ru ions, Zn ions, and Ni ions, and bis (terpyridyl) benzene.
- a step of forming a film on a substrate by a membrane method proton conductivity (room temperature, 95% RH) is 3 ⁇ 10 ⁇ 2 Scm ⁇ 1 or more, and proton conductivity usable in a neutral solvent atmosphere
- the membrane can be manufactured easily.
- the humidity sensor of the present invention includes a substrate, two electrodes formed on one surface of the substrate so as to be separated from each other, and a film formed so as to cover the two electrodes on the one surface. Since it is the structure which is a highly proton conductive polymer film as described in (1) or (2), it can be set as a highly sensitive humidity sensor.
- FIG. 1B is a cross-sectional view taken along the line A-A ′ of the humidity sensor of FIG. 1A. It is the schematic which shows an example of the state of the area
- the high proton conductive polymer film according to an embodiment of the present invention includes one or more metal ions selected from the group of Fe ions, Co ions, Ru ions, Zn ions, and Ni ions, and bis (terpyridyl). This is an organic / metal hybrid polymer film composed of benzene supramolecules.
- the organic / metal hybrid polymer is represented by the general formula (1) described above.
- M is one or more metal ions selected from the group of Fe ions, Co ions, Ru ions, Zn ions, and Ni ions, and n is an integer of 5 or more and 1000 or less.
- the organic / metal hybrid polymer is represented by the formulas (2) and (3).
- a method for producing a highly proton conductive polymer film according to an embodiment of the present invention includes any one or more metal ions selected from the group consisting of Fe ions, Co ions, Ru ions, Zn ions, and Ni ions, and bismuth.
- the solvent is water or an organic solvent and a mixture thereof, and the organic solvent is any selected from the group consisting of alcohol, acetonitrile, dimethyl sulfoxide, and dimethylformamide.
- the alcohol include methanol and ethanol.
- spin coating it is preferable to have a low-speed rotation process and a high-speed rotation process. For example, first rotate at 400 rpm for 120 seconds and then rotate at 500 rpm for 160 seconds. Thereby, a uniform and flat film can be formed.
- FIGS. 1A and 1B are schematic diagrams illustrating an example of a humidity sensor according to an embodiment of the present invention.
- 1A is a plan view
- FIG. 1B is a cross-sectional view taken along the line AA ′.
- the humidity sensor 1 includes a substrate 41, two electrodes 31 and 32 formed on one surface of the substrate 41 at a distance l, and the two electrodes 31 on the one surface. And a film 11 formed to cover 32.
- the film 11 is the high proton conductive polymer film described above.
- the electrodes 31 and 32 are connected to a power source 36 via a wiring 34. By operating the power source 36, a voltage can be applied to the region 11 c between the electrodes 31 and 32 of the film 11.
- FIG. 2 is a schematic diagram showing an example of a state of an inter-electrode region of a high proton conductive polymer film when a voltage is applied in a 95% RH atmosphere by a humidity sensor using a film made of Fe polymer. .
- a region made of Fe (III) appears in the vicinity of one of the electrodes. Thereby, proton conductivity is improved.
- the high proton conductive polymer film which is embodiment of this invention can also be used for a solid polymer fuel cell.
- a polymer electrolyte fuel cell according to an embodiment of the present invention includes a cathode electrode, an anode electrode disposed so as to face the cathode electrode, and an electrolyte sandwiched between the two electrodes.
- the high proton conductive polymer film, the production method thereof, and the humidity sensor which are the embodiments of the present invention are not limited to the above-described embodiments, and various modifications are made within the scope of the technical idea of the present invention. be able to. Specific examples of this embodiment are shown in the following examples. However, the present invention is not limited to these examples.
- Example 1 [Preparation of conductivity measurement sample] First, a quartz substrate having a rectangular shape in plan view provided with eight electrodes on one surface was prepared. Four of these electrodes are connected to a power supply connection portion having a rectangular shape in plan view on one side, and the other four are connected to a power supply connection portion having a rectangular shape in plan view on the other side. Each of the electrodes is in a planar view between two rectangular substrate center mark portions in a planar view, and four electrodes are extended from the power connection portion on one side and 4 are extended from the power connection portion on the other side.
- the books are arranged so as to mesh with each other, and are parallel to each other at the meshing portions. The length (electrode width) of the parallel part is 2.5 mm.
- the electrode spacing is different between 10 ⁇ m and 250 ⁇ m.
- an Fe polymer (organic / metal hybrid polymer) was dispersed in ethanol at a concentration of 100 mg / L to prepare a mixed solution.
- the substrate was washed with acetone for 2 minutes with acetone and then with isopropanol to remove residual water and dust on the electrode surface of the substrate and then blown with nitrogen gas.
- 10 ml of the mixed solution was formed on one surface of the substrate so as to cover the electrode by a spin coating method.
- the spin coating was performed under the condition of first rotating at 400 rpm for 120 seconds and then rotating at 500 rpm for 160 seconds.
- FIG. 3 is a photograph showing a substrate with an electrode used in this example and a polymer film formed thereon, and is an overall photograph (a) and a partially enlarged photograph (b). Since the polymer film is transparent, the film forming portion is indicated by an arrow.
- Example 2 A conductivity measurement sample of Example 2 was prepared in the same manner as in Example 1 except that a mixed solution was prepared using Ru polymer (organic / metal hybrid polymer) dispersed in ethanol at a concentration of 250 mg / L. did.
- Example 3 The conductivity measurement sample of Example 3 was prepared in the same manner as in Example 1 except that a mixed solution was prepared using a Zn polymer (organic / metal hybrid polymer) dispersed in ethanol at a concentration of 250 mg / L. Produced.
- Example 4 A conductivity measurement sample of Example 4 was prepared in the same manner as in Example 1 except that a mixed solution was prepared using a Co polymer (organic / metal hybrid polymer) dispersed in ethanol at a concentration of 100 mg / L. did.
- Example 5 A conductivity measurement sample of Example 5 was prepared in the same manner as in Example 1 except that a mixed solution was prepared by using Ni polymer (organic / metal hybrid polymer) and dispersing in ethanol at a concentration of 100 mg / L. did. Each conductivity measurement sample was stored in a closed container (chamber) until each measurement was performed and while each condition was changed and each measurement was performed.
- the thickness of each polymer film was measured with an ellipsometer. First, casting was performed at a concentration of 500 mg / L to prepare a reference sample with a thick film thickness of each polymer film, and optical constants of each polymer film were determined. Next, using these optical constant values, data fitting was performed using a general oscillator model, and the thickness of each polymer film was calculated. The thickness of each polymer film of Fe, Ru, Zn, Co, and Ni was calculated to be 4.5 nm, 6.8 nm, 20.0 nm, 6.4 nm, and 6.1 nm, respectively.
- the conductivity of the polymer film was measured using a Solartron 1287 (consisting of a potentiostat and a frequency response analysis system (1260 frequency response analyzer system)).
- the polymer film resistance value was calculated from the impedance plot (Nyquist plot) under the conditions of “frequency range 50 Hz to 5 MHz, amplitude 10 mV ac or 1.0 V dc bias”. From the obtained resistance value, the proton conductivity of the polymer was calculated using the following equation.
- FIG. 4A to 4D are impedance plots (Nyquist plots) of the Fe polymer film. It is a plot under 95% RH conditions.
- FIG. 4A is a plot with Z real ⁇ 10 5 in the range of 0-4. Raw (raw data) is indicated by a filled square, and fitting (fitting data) is indicated by an unfilled square. Similarly, a filled mark indicates raw data, and an unfilled mark indicates fitting data.
- FIG. 4B is a plot with Z real ⁇ 10 5 ranging from 0 to 0.6.
- FIG. 4C is a plot of Z real ⁇ 10 5 in the range of 0 to 45 when a different dc bias from 0.1 V to 2.0 V is applied.
- FIG. 4D is a plot with Z real ⁇ 10 5 ranging from 0 to 1.0.
- FIG. 5 is a Nyquist plot for an Fe polymer film at 58% RH at room temperature.
- FIG. 6A-6C are Nyquist plots of Ru polymer films.
- FIG. 6A is a Nyquist plot under 95% RH conditions.
- FIG. 6B is a Nyquist plot at different dc biases, and
- FIG. 6C is a plot with Z real ⁇ 10 6 ranging from 0 to 0.15.
- FIG. 7A-7C are Nyquist plots of Zn polymer films.
- FIG. 7A is a Nyquist plot of a Zn polymer film under 95% RH conditions.
- FIG. 7B is a Nyquist plot of a Zn polymer film at different dc biases, and
- FIG. 7C is a plot with Z real ⁇ 10 6 ranging from 0 to 0.11.
- FIG. 8 is a Nyquist plot of the Co polymer film. It is a Nyquist plot of Co polymer film under 95% RH condition.
- FIG. 9 is a Nyquist plot of the Ni polymer film. It is a Nyquist plot of Ni polymer film under 95% RH condition.
- FIG. 10 is a graph showing an example of the measured leakage current.
- FIG. 11 is the IV characteristic of the Fe polymer film at 95% RH.
- FIG. 12 shows IV characteristics of the Fe polymer film under reduced pressure and in the air (28% RH).
- FIG. 13 is an IV characteristic of an Fe polymer film in air (28% RH) after 95% RH experiment. The sweep goes from -3.0V to 3.0V and back to -3.0V again.
- FIG. 14 is an IV characteristic of an Fe polymer film in the air (28% RH) after the 95% RH experiment. The sweep goes from -5.0V to 5.0V and back to -5.0V again. The current was positive in both directions.
- FIG. 15 shows IV characteristics of the Fe polymer film at a sweep rate of 1 s delay (a), 5 s delay (b), and 20 s delay (c). All experiments were performed in air (28% RH) after the experiment in 95% RH. The current increased with increasing sweep speed.
- FIG. 16 is an IV characteristic of a Ru polymer film in air (28% RH) after 95% RH experiment. No change in current was observed.
- FIG. 17A and FIG. 17B are graphs showing the IV characteristics of the Ru polymer film.
- FIG. 17A is an IV characteristic of a Ru polymer film under reduced pressure and in air (28% RH). The sweep direction is -2.0V to 2.0V.
- FIG. 17B is the IV characteristic of a Ru polymer film in 95% RH.
- FIG. 18 is an IV characteristic of a Zn polymer film at 95% RH.
- the proton conductive polymer film of the present invention, the production method thereof, and the humidity sensor have a proton conductivity (room temperature, 95% RH) of 3 ⁇ 10 ⁇ 2 Scm ⁇ 1 or more and can be used in a neutral solvent atmosphere.
- the present invention relates to a membrane and can be used as a highly sensitive humidity sensor or a proton exchange membrane of a polymer electrolyte fuel cell, and may be used in the humidity sensor industry, the fuel cell industry, and the like.
Abstract
Description
本願は、2012年8月1日に、日本に出願された特願2012-171062号に基づき優先権を主張し、その内容をここに援用する。
プロトン伝導度の高い材料は、電流電圧特性が湿度に高感度に変動し、高湿度において伝導度が上がる材料である。
特許文献1は、銅イオンを含む配位高分子金属錯体に関するものである。これらの銅イオンを含む配位高分子金属錯体は、電流電圧特性が湿度に高感度に変動し、高湿度において伝導度が上がるので、これらの材料がプロトン伝導度の高い材料である。
高プロトン伝導性ポリマーフィルムは、例えば、燃料電池や湿度センサーのプロトン交換膜として用いられる(特許文献1~3)。
具体的には、ナフィオン112、115、117のプロトン伝導度(30℃、2端子法)は約0.038~0.047Scm-1であることが開示されている(非特許文献8)。
インピーダンス・スペクトロスコピーによるプロトン交換膜の伝導率の測定もされている(非特許文献10)。また、ナフィオン膜のインピーダンスの測定結果、ナフィオン膜の伝導率(室温、100%RH)は0.073Scm-1であることが開示されている(非特許文献11)。
非特許文献1に記載のPCPsのプロトン伝導度(298K、95%RH)は2.3×10-9~2.0×10-6Scm-1である(例えば、非特許文献1のTable.1を参照)。
BZY(BaZr0.8Y0.2O3-δ)膜の伝導率(500℃)は0.11Scm-1である(非特許文献12)。
Ca-doped LaNbO4膜の伝導率(800℃、wet atmospheres)は約10-3Scm-1である(非特許文献13)。
更にまた、ナフィオンについては、それ自体が強酸性であるので、中性溶媒雰囲気で使用ができないという問題があった。
本発明は、以下の構成を有する。
以下、添付図面を参照しながら、本発明の実施形態である高プロトン伝導性ポリマーフィルム、その製造方法及び湿度センサーについて説明する。
まず、本発明の実施形態である高プロトン伝導性ポリマーフィルムについて説明する。
本発明の実施形態である高プロトン伝導性ポリマーフィルムは、Feイオン、Coイオン、Ruイオン、Znイオン、Niイオンの群から選択されるいずれか1又は2以上の金属イオンと、ビス(ターピリジル)ベンゼンの超分子とからなる有機/金属ハイブリッドポリマーのフィルムである。
式(1)で、MはFeイオン、Coイオン、Ruイオン、Znイオン、Niイオンの群から選択されるいずれか1又は2以上の金属イオンであり、nは5以上1000以下の整数である。
例えば、前記有機/金属ハイブリッドポリマーは、式(2)、(3)で表される。
次に、本発明の実施形態である高プロトン伝導性ポリマーフィルムの製造方法について説明する。
本発明の実施形態である高プロトン伝導性ポリマーフィルムの製造方法は、Feイオン、Coイオン、Ruイオン、Znイオン、Niイオンの群から選択されるいずれか1又は2以上の金属イオンと、ビス(ターピリジル)ベンゼンの超分子とからなる有機/金属ハイブリッドポリマーを10~1000mg/Lの濃度で溶媒に分散させて混合溶液を調製する工程と、前記混合溶液をキャスト法、ディッピング法又はスピンコーティング法のいずれか一の湿式成膜法により基板上に成膜する工程と、を有する。
アルコールとしては、メタノール、エタノール等を挙げることができる。
次に、本発明の実施形態である湿度センサーについて説明する。
図1Aおよび図1Bは、本発明の実施形態である湿度センサーの一例を示す概略図である。図1Aは平面図、図1BはA-A’線における断面図である。
図1Aおよび図1Bに示すように、湿度センサー1は、基板41と、基板41の一面に距離lで離間して形成された2つの電極31、32と、前記一面で、2つの電極31、32を覆うように形成されたフィルム11と、を有する。
フィルム11は、先に記載の高プロトン伝導性ポリマーフィルムである。
電源36を操作することにより、フィルム11の電極31、32間の領域11cに電圧を印加することができる。
電圧を印加すると、一方の電極の近傍にFe(III)とされた領域が発現する。これにより、プロトン伝導性が高められる。
本発明の実施形態である固体高分子型燃料電池は、カソード電極と、前記カソード電極と対向するように配置したアノード電極と、該両電極に挟まれた電解質を有し、前記電解質が先に記載の高プロトン伝導性ポリマーフィルムである。
この固体高分子型燃料電池は、高プロトン伝導性ポリマーフィルムを電解質として用いているので、蓄電性の高い燃料電池として用いることができる。
[伝導度測定用サンプル作製]
まず、8つの電極を一面上に設けた平面視矩形状の石英基板を用意した。
これらの電極のうち4つは一辺側の平面視矩形状の電源接続部に接続されており、他の4つは他辺側の平面視矩形状の電源接続部に接続されている。
電極はいずれも2つの平面視矩形状の基板中心マーク部の間で平面視線状とされ、一辺側の電源接続部から延伸された4本と、他辺側の電源接続部から延伸された4本が互いにかみ合うように配置され、かつ、かみ合う部分で互いに平行とされている。平行とされた部分の長さ(電極幅)は2.5mmである。また、電極間隔は10μm~250μmの間でそれぞれ異なるものとされている。これにより、基板中心マーク部の間の電極を覆うようにフィルムを形成したとき、一辺側のいずれかの電源接続部と、他辺側のいずれかの電源接続部をそれぞれ電源に接続して、フィルムに電圧を印加することにより、異なる電極間隔でフィルムの電流電圧特性を測定できる。
その後すぐに、混合溶液を10ml、電極を覆うように基板の一面に、スピンコーティング法によりポリマーフィルムを成膜した。スピンコーティングは、最初に120秒間400rpmで回転させ、次に160秒間500rpmで回転させる条件とした。
以上により、実施例1の伝導度測定用サンプルを作製した。
図3は、本実施例で用いた電極付き基板と、それに成膜したポリマーフィルムを示す写真であって、全体写真(a)と、部分拡大写真(b)である。ポリマーフィルムは透明であるので、成膜部分を矢印で示している。
Ruポリマー(有機/金属ハイブリッドポリマー)を用い、エタノールに250mg/Lの濃度で分散して、混合溶液を調製した他は実施例1と同様にして、実施例2の伝導度測定用サンプルを作製した。
Znポリマー(有機/金属ハイブリッドポリマー)を用い、エタノールに250 mg/Lの濃度で分散して、混合溶液を調製した他は実施例1と同様にして、実施例3の伝導度測定用サンプルを作製した。
Coポリマー(有機/金属ハイブリッドポリマー)を用い、エタノールに100mg/Lの濃度で分散して、混合溶液を調製した他は実施例1と同様にして、実施例4の伝導度測定用サンプルを作製した。
Niポリマー(有機/金属ハイブリッドポリマー)を用い、エタノールに100mg/Lの濃度で分散して、混合溶液を調製した他は実施例1と同様にして、実施例5の伝導度測定用サンプルを作製した。
各伝導度測定用サンプルは、それぞれの測定を行うまで、また、条件を変更して各測定を行う間は、閉鎖系コンテナ(チャンバー)内で貯蔵した。
各ポリマーフィルムの厚さは、エリプソメーター(ellipsometer)により測定した。
まず、500mg/Lの濃度でキャストして、各ポリマーフィルムの膜厚が厚いリファレンス・サンプルを作成し、各ポリマーフィルムの光学定数(optical constants)を決定した。
次に、これらの光学定数の値を用い、一般的なオシレーターモデルでデータフィットして、各ポリマーフィルムの厚さを算出した。
Fe、Ru、Zn、Co、Niの各ポリマーフィルムの厚さは、それぞれ4.5nm、6.8nm、20.0nm、6.4nm、6.1nmと算出された。
ポリマーフィルムの伝導度は、ソラートロン1287(Solartron 1287:ポテンシオスタット(potentiostat)と周波数反応分析システム(1260 frequency response analyzer system)からなる)を用いて測定した。
「周波数範囲50Hz~5MHz、振幅10mVのac又は1.0Vのdcバイアス」の条件で、インピーダンスプロット(ナイキストプロット)からポリマーフィルム抵抗値を算出した。求めた抵抗値から、以下の式を用いてポリマーのプロトン導電性を算出した。
ポリマーのプロトン導電性(σ)/Scm-1 =(1/R)×(l/A)
ここで、
R=ナイキストプロットから求めた抵抗値、
l=電極間距離、
A=ポリマー膜の断面積(ポリマーの膜厚から算出)である。
図4Aから図4Dは、Feポリマーフィルムのインピーダンスプロット(ナイキストプロット)である。95%RH条件下のプロットである。図4AはZreal×105が0~4の範囲のプロットである。Raw(生データ)は、塗りつぶした四角で示しており、Fitting(フィッティングデータ)は、塗りつぶさない四角で示している。以下同様に、塗りつぶしたマークは生データを示し、塗りつぶさないマークはフィッティングデータを示す。
図4Bは、Zreal×105が0~0.6の範囲のプロットである。
また、図4Cは0.1Vから2.0Vまで異なるdcバイアスを印加した時のZreal×105が0~45の範囲のプロットである。dcバイアス0.1Vが四角、0.5Vが丸、1.0Vが三角、1.5Vがひし形、2.0Vが星型を示す(以下、同様)。
図4Dは、Zreal×105が0~1.0の範囲のプロットである。
図5は、58%RH、室温条件下のFeポリマーフィルムのナイキストプロットである。
図6Aから図6Cは、Ruポリマーフィルムのナイキストプロットである。図6Aは95%RH条件下のナイキストプロットである。図6Bは、異なるdcバイアスでのナイキストプロットであり、図6Cは、Zreal×106が0~0.15の範囲のプロットである。
図7Aから図7Cは、Znポリマーフィルムのナイキストプロットである。図7Aは95%RH条件下のZnポリマーフィルムのナイキストプロットである。図7Bは異なるdcバイアスでのZnポリマーフィルムのナイキストプロットであり、図7Cは、Zreal×106が0~0.11の範囲のプロットである。
図8は、Coポリマーフィルムのナイキストプロットである。95%RH条件下のCoポリマーフィルムのナイキストプロットである。
図9は、Niポリマーフィルムのナイキストプロットである。95%RH条件下のNiポリマーフィルムのナイキストプロットである。
ポリマーフィルムのI-V特性測定には、標準的な半導体特性評価システムであるKeithley 4200-SCSを用いた。
得られたI-Vデータからポリマーフィルムの平均漏れ電流(leakage current)を抽出した。
図10は、測定された漏れ電流の一例を示すグラフである。
図11は、95%RHでのFeポリマーフィルムのI-V特性である。
図12は、減圧下と大気中(28%RH)のFeポリマーフィルムのI-V特性である。
図14は、95%RHの実験後、大気中(28%RH)のFeポリマーフィルムのI-V特性である。スイープは-5.0Vから5.0Vまで行き、再び-5.0Vに戻る。
両方向で電流がプラスとなった。
すべての実験は95%RH中の実験後、大気中(28%RH)で実施した。
電流はスイープ速度の増加とともに増加した。
図16は、95%RHの実験後、大気中(28%RH)のRuポリマーフィルムのI-V特性である。
電流変化がみられなかった。
図18は、95%RHでのZnポリマーフィルムのI-V特性である。
11 高プロトン伝導性ポリマーフィルム
11c 高プロトン伝導性ポリマーフィルムの電極間領域
31、32 電極
34 配線
36 電源
41 基板
Claims (5)
- Feイオン、Coイオン、Ruイオン、Znイオン、Niイオンの群から選択されるいずれか1又は2以上の金属イオンと、ビス(ターピリジル)ベンゼンとからなる有機/金属ハイブリッドポリマーのフィルムであることを特徴とする高プロトン伝導性ポリマーフィルム。
- Feイオン、Coイオン、Ruイオン、Znイオン、Niイオンの群から選択されるいずれか1又は2以上の金属イオンと、ビス(ターピリジル)ベンゼンとからなる有機/金属ハイブリッドポリマーを10~1000mg/Lの濃度で溶媒に分散させて混合溶液を調製する工程と、
前記混合溶液をキャスト法、ディッピング法又はスピンコーティング法のいずれか一の湿式成膜法により基板上に成膜する工程と、を有することを特徴とする高プロトン伝導性ポリマーフィルムの製造方法。 - 前記溶媒が水又は有機溶媒及びこれらの混合物であり、
前記有機溶媒が、アルコール、アセトニトリル、ジメチルスルホキシド、ジメチルホルムアミドの群から選択されるいずれかであることを特徴とする請求項3に記載の高プロトン伝導性ポリマーフィルムの製造方法。 - 基板と、
前記基板の一面に離間して形成された2つの電極と、
前記一面で、前記2つの電極を覆うように形成されたフィルムと、を有し、
前記フィルムが請求項1又は2に記載の高プロトン伝導性ポリマーフィルムであることを特徴とする湿度センサー。
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- 2013-07-26 US US14/374,985 patent/US20150021180A1/en not_active Abandoned
- 2013-07-26 WO PCT/JP2013/070299 patent/WO2014021208A1/ja active Application Filing
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EP3138868A4 (en) * | 2014-05-02 | 2017-09-27 | National Institute for Materials Science | Organic/heterometallic hybrid polymer, process for producing same, film of organic/heterometallic hybrid polymer, organic/multimetallic hybrid polymer, process for producing same, and film of organic/multimetallic hybrid polymer |
US10118995B2 (en) | 2014-05-02 | 2018-11-06 | National Institute Of Materials Science | Organic/heterometallic hybrid polymer, process for producing same, film of organic/heterometallic hybrid polymer, organic/multimetallic hybrid polymer, process for producing same, and film of organic/multimetallic hybrid polymer |
WO2016185679A1 (ja) * | 2015-05-15 | 2016-11-24 | パナソニック株式会社 | 化学センサ |
Also Published As
Publication number | Publication date |
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JP5765692B2 (ja) | 2015-08-19 |
JPWO2014021208A1 (ja) | 2016-07-21 |
EP2796488A1 (en) | 2014-10-29 |
EP2796488A4 (en) | 2014-11-26 |
US20150021180A1 (en) | 2015-01-22 |
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