JP6187962B2 - Anode catalyst for alkaline direct ethanol fuel cell, alkaline direct ethanol fuel cell provided with the catalyst, method for producing the catalyst, and method for improving output of alkaline direct ethanol fuel cell - Google Patents
Anode catalyst for alkaline direct ethanol fuel cell, alkaline direct ethanol fuel cell provided with the catalyst, method for producing the catalyst, and method for improving output of alkaline direct ethanol fuel cell Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 178
- 239000003054 catalyst Substances 0.000 title claims description 109
- 239000000446 fuel Substances 0.000 title claims description 93
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 12
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 75
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 74
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 86
- 229910052697 platinum Inorganic materials 0.000 description 42
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000010718 Oxidation Activity Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000012670 alkaline solution Substances 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 238000003487 electrochemical reaction Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- -1 hydroxide ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- 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
Description
本発明は、アルカリ直接型エタノール燃料電池（アルカリ形電解質が用いられるとともに、アノードに燃料としてエタノールが供給される燃料電池）のアノード触媒に関する。 The present invention relates to an anode catalyst for an alkaline direct ethanol fuel cell (a fuel cell in which an alkaline electrolyte is used and ethanol is supplied to the anode as fuel).
燃料電池は、電解質層（固体電解質膜或いは電解液層）と、電解質層の両面にそれぞれ配設される電極（アノード及びカソード）とを備える膜電極構造体（ＭＥＡ）で電気化学反応を起こし、当該電気化学反応により発生した電気エネルギーを外部に取り出す装置である。 A fuel cell causes an electrochemical reaction in a membrane electrode structure (MEA) including an electrolyte layer (a solid electrolyte membrane or an electrolyte layer) and electrodes (anode and cathode) respectively disposed on both sides of the electrolyte layer. It is a device for taking out electrical energy generated by the electrochemical reaction to the outside.
燃料電池の一つに固体高分子形燃料電池（ＰＥＦＣ）がある。ＰＥＦＣは、低温領域で運転可能であるとともに、高いエネルギー変換効率を示し、起動時間が短く、且つ、システムが小型軽量であることから、電気自動車の動力源や携帯用電源として注目されている。 One type of fuel cell is a polymer electrolyte fuel cell (PEFC). PEFC has been attracting attention as a power source and a portable power source for electric vehicles because it can be operated in a low temperature region, exhibits high energy conversion efficiency, has a short start-up time, and has a small and lightweight system.
しかしながら、ＰＥＦＣの燃料としては水素が用いられており、その製造コストや貯蔵の問題は未だ解決されていない。そのため、水素に替わる「次世代燃料電池の燃料」として炭化水素系燃料の適用が試みられており、例えば、メタノールやエタノール等のアルコール系燃料が注目されている。 However, hydrogen is used as the fuel for PEFC, and the production cost and storage problems have not been solved yet. For this reason, application of hydrocarbon fuels as “next-generation fuel cell fuels” to replace hydrogen has been attempted. For example, alcohol fuels such as methanol and ethanol have attracted attention.
燃料電池の燃料としてアルコール系燃料を用いる場合、燃料電池のアノードにおいて触媒被毒を抑えつつ如何に効率的に燃料を酸化させるかが重要となる。すなわち、アノード触媒の性能向上が一つの課題となっている。この観点から、本発明者らは燃料電池のアノード触媒について鋭意研究し、特許文献１において、特に直接型メタノール燃料電池の性能を飛躍的に向上させることが可能なアノード触媒について開示した。 When an alcohol fuel is used as a fuel for a fuel cell, it is important how to efficiently oxidize the fuel while suppressing catalyst poisoning at the anode of the fuel cell. That is, improving the performance of the anode catalyst has become one issue. From this point of view, the present inventors have intensively studied the anode catalyst of the fuel cell, and disclosed in Patent Document 1 an anode catalyst capable of dramatically improving the performance of the direct methanol fuel cell.
しかしながら、特許文献１に開示された燃料電池は、水素イオン伝導性を有する固体電解質膜を用いることを想定したもので、燃料電池の作動環境が酸性となる。そのため、アノード触媒としては酸腐食の問題のない貴金属を用いる必要があり、コストが増大するという問題があった。 However, the fuel cell disclosed in Patent Document 1 assumes that a solid electrolyte membrane having hydrogen ion conductivity is used, and the operating environment of the fuel cell becomes acidic. Therefore, it is necessary to use a noble metal that does not have a problem of acid corrosion as the anode catalyst, and there is a problem that the cost increases.
上記の問題に鑑み、本発明者らは、水酸化物イオン伝導性を有する固体電解質膜或いはアルカリ溶液を用いたアルカリ燃料電池について着目した。アルカリ燃料電池であれば、作動環境がマイルドになり、電極材料にＮｉやＦｅ等の金属を用いることができ、貴金属の使用量を削減することができると考えられる。また、本発明者らは、水素に替わる次世代燃料電池の燃料として、エタノールに着目した。エタノールはメタノールに比べて毒性が低く、バイオマスからも製造可能であることから、製造コストや貯蔵の問題が少ない。 In view of the above problems, the present inventors paid attention to an alkaline fuel cell using a solid electrolyte membrane or an alkaline solution having hydroxide ion conductivity. In the case of an alkaline fuel cell, the operating environment is mild, and metals such as Ni and Fe can be used as the electrode material, and the amount of noble metal used can be reduced. In addition, the present inventors have focused on ethanol as a fuel for a next-generation fuel cell that replaces hydrogen. Since ethanol is less toxic than methanol and can be produced from biomass, there are few production costs and storage problems.
このように、エタノールを燃料として用い、貴金属の使用量を出来るだけ削減した「アルカリ直接型エタノール燃料電池」の開発は、化石燃料の枯渇や貴金属を含めたレアメタル資源戦略が喫緊の課題となっている現在において、極めて重要といえる。 In this way, the development of an “alkali direct ethanol fuel cell” that uses ethanol as a fuel and reduces the amount of precious metal used as much as possible has become an urgent issue for the depletion of fossil fuels and the rare metal resource strategy including precious metals It can be said that it is extremely important at present.
アルカリ直接型エタノール燃料電池にあっても、やはりアノード触媒の性能を向上させることが課題の一つとなる。現状では、アルカリ直接型エタノール燃料電池のアノード触媒として白金−ルテニウム系触媒が想定されているが、その性能は充分なものとはいえない。 Even in an alkaline direct ethanol fuel cell, improving the performance of the anode catalyst is still one of the problems. At present, a platinum-ruthenium-based catalyst is assumed as an anode catalyst for an alkaline direct ethanol fuel cell, but its performance is not sufficient.
そこで本発明は、アルカリ直接型エタノール燃料電池の性能を向上させることが可能なアノード触媒を提供することを課題とする。 Accordingly, an object of the present invention is to provide an anode catalyst capable of improving the performance of an alkaline direct ethanol fuel cell.
鋭意研究を進めた結果、本発明者らは、アノード触媒として、白金酸化物を還元してなる白金部分酸化物を用いることで、白金−ルテニウム系触媒或いは単なる白金触媒よりも貴金属使用量を削減しつつ、アルカリ直接型エタノール燃料電池の性能を向上させることが可能であることを知見した。 As a result of diligent research, the present inventors reduced the amount of noble metal used compared to platinum-ruthenium-based catalysts or simple platinum catalysts by using platinum partial oxides obtained by reducing platinum oxide as anode catalysts. However, it has been found that the performance of the alkaline direct ethanol fuel cell can be improved.
本発明は上記知見に基づいてなされたものである。すなわち、
第１の本発明は、白金酸化物を還元することにより得られる、アルカリ直接型エタノール燃料電池用アノード触媒である。
The present invention has been made based on the above findings. That is,
1st this invention is an anode catalyst for alkaline direct ethanol fuel cells obtained by reduce | restoring a platinum oxide.
本発明において「還元」とは、白金酸化物が白金（純金属）となるまで完全に還元することを意味するものではなく、白金酸化物を部分還元する主旨である。すなわち、還元後に得られるアノード触媒が白金の部分酸化物により構成されることを意味する。本発明において「還元」とは、水素等の還元ガスを用いた還元、電気化学還元（電解還元）等、白金酸化物を還元可能な処理であれば、いずれも適用可能である。 In the present invention, “reduction” does not mean that platinum oxide is completely reduced to platinum (pure metal), but is intended to partially reduce platinum oxide. That is, it means that the anode catalyst obtained after the reduction is composed of a partial oxide of platinum. In the present invention, “reduction” is applicable to any treatment capable of reducing platinum oxide, such as reduction using a reducing gas such as hydrogen, electrochemical reduction (electrolytic reduction), and the like.
特に、第１の本発明に係るアノード触媒は、白金酸化物を電気化学還元して得られるものであることが好ましい。操作が簡便であり、また、還元の制御が容易だからである。 In particular, the anode catalyst according to the first aspect of the present invention is preferably obtained by electrochemical reduction of platinum oxide. This is because the operation is simple and the reduction control is easy.
第２の本発明は、第１の本発明に係るアルカリ直接型エタノール燃料電池用アノード触媒を備えた、アルカリ直接型エタノール燃料電池である。 The second present invention is an alkaline direct ethanol fuel cell comprising the anode catalyst for an alkaline direct ethanol fuel cell according to the first present invention.
第３の本発明は、白金酸化物を還元する還元工程を備える、アルカリ直接型エタノール燃料電池用アノード触媒の製造方法である。 3rd this invention is a manufacturing method of the anode catalyst for alkaline direct ethanol fuel cells provided with the reduction process which reduces a platinum oxide.
第３の本発明において、還元工程が、白金酸化物に電気化学還元を施す工程であることが好ましい。 In the third aspect of the present invention, the reduction step is preferably a step of subjecting platinum oxide to electrochemical reduction.
第４の本発明は、アノードに触媒として白金酸化物を備えるアルカリ直接型エタノール燃料電池において、白金酸化物を還元する還元工程を備える、アルカリ直接型エタノール燃料電池の出力向上方法である。 The fourth aspect of the present invention is a method for improving the output of an alkaline direct ethanol fuel cell comprising a reduction step of reducing platinum oxide in an alkaline direct ethanol fuel cell having platinum oxide as a catalyst at the anode.
第４の本発明において、「アノードに触媒として白金酸化物を備える」とは、燃料電池作製時点（作製直後）からアノード触媒として白金酸化物を備える形態に限定されない。例えば、アノードに触媒として白金（純金属）を備える燃料電池に対して、白金を意図的に酸化させて白金酸化物とする形態、或いは、経年劣化等によって白金触媒が自然に酸化された形態をも含む概念である。 In the fourth aspect of the present invention, “having platinum oxide as a catalyst in the anode” is not limited to a form in which platinum oxide is provided as an anode catalyst from the time of fuel cell production (immediately after production). For example, for a fuel cell having platinum (pure metal) as a catalyst at the anode, a form in which platinum is intentionally oxidized to form platinum oxide, or a form in which the platinum catalyst is naturally oxidized due to aging, etc. It is a concept that also includes
第４の本発明において、還元工程が、白金酸化物に電気化学還元を施す工程であることが好ましい。燃料電池の電気回路を有効に利用しつつ、容易に白金酸化物を還元することが可能だからである。 In the fourth aspect of the present invention, the reduction step is preferably a step of subjecting platinum oxide to electrochemical reduction. This is because it is possible to easily reduce platinum oxide while effectively using the electric circuit of the fuel cell.
本発明によれば、アルカリ直接型エタノール燃料電池の性能を向上させることが可能なアノード触媒を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the anode catalyst which can improve the performance of an alkaline direct ethanol fuel cell can be provided.
１．アルカリ直接型エタノール燃料電池用アノード触媒
本発明に係るアルカリ直接型エタノール燃料電池用アノード触媒は、白金酸化物を還元することにより得られる。「還元」とは、白金酸化物が白金（純金属）となるまで完全に還元することを意味するものではなく、白金酸化物を部分還元する主旨である。すなわち、還元後において触媒中に一部の酸素が意図的に残されている状態を意味する。
1. Anode catalyst for alkaline direct ethanol fuel cell The anode catalyst for alkaline direct ethanol fuel cell according to the present invention is obtained by reducing platinum oxide. “Reduction” does not mean that platinum oxide is completely reduced until it becomes platinum (pure metal), but is intended to partially reduce platinum oxide. That is, it means a state in which some oxygen is intentionally left in the catalyst after the reduction.
還元前の白金酸化物としては、一酸化白金や二酸化白金、或いはこれらの混合物等を用いることができる。本発明では、このような白金酸化物を還元することにより、アルカリ条件下におけるエタノール酸化活性が飛躍的に増大されたアノード触媒を得ることができる。特に、ＰｔＯｘ（ｘは０．０５以上０．５以下）で示される部分酸化物となるまで還元することが好ましい。ｘについては、より好ましくは０．０５以上０．４以下、さらに好ましくは０．０５以上０．３以下、特に好ましくは０．０５以上０．２以下である。白金酸化物の還元が過剰（ｘがほぼ０）な場合、或いは過小（ｘが１〜２）な場合、エタノール酸化活性の向上効果が得られ難い。 As the platinum oxide before reduction, platinum monoxide, platinum dioxide, or a mixture thereof can be used. In the present invention, by reducing such platinum oxide, it is possible to obtain an anode catalyst in which ethanol oxidation activity under alkaline conditions is dramatically increased. In particular, it is preferable to reduce until it becomes a partial oxide represented by PtO x (x is 0.05 or more and 0.5 or less). x is more preferably 0.05 or more and 0.4 or less, further preferably 0.05 or more and 0.3 or less, and particularly preferably 0.05 or more and 0.2 or less. When the reduction of the platinum oxide is excessive (x is substantially 0) or is excessive (x is 1 to 2), it is difficult to obtain an effect of improving the ethanol oxidation activity.
還元前の白金酸化物は、粉末状、膜状等、種々の形態のものを適用することができる。還元後の触媒についても同様で、粉末状、膜状等、いずれの形態であってもよい。ただし、粉末状のものが、アルカリ直接型エタノール燃料電池のアノード触媒として最も好適である。 The platinum oxide before reduction can be applied in various forms such as powder and film. The same applies to the catalyst after reduction, and any form such as powder or film may be used. However, powder is most suitable as an anode catalyst for an alkaline direct ethanol fuel cell.
白金酸化物を還元する手法としては、水素等の還元ガスを用いた還元、電気化学還元（電解還元）等、種々の手法を適用することができる。特に、簡便且つ還元の制御が容易であることから、電気化学還元が好ましい。後述するアルカリ直接型エタノール燃料電池の出力向上方法とも関連するが、アノードに触媒として白金酸化物を備えるアルカリ直接型エタノール燃料電池において、アノードに還元電流を流すことで、白金酸化物を還元することもできる。或いは、アノードを還元ガスに曝す等、電気化学還元によらずに白金酸化物を還元してもよい。すなわち、本発明に係るアノード触媒は、アノードに備えられた白金酸化物を燃料電池作製後に還元して得られる形態をも含む。 As a method for reducing platinum oxide, various methods such as reduction using a reducing gas such as hydrogen, electrochemical reduction (electrolytic reduction), and the like can be applied. In particular, electrochemical reduction is preferred because it is simple and easy to control the reduction. Although related to the output improvement method of an alkaline direct ethanol fuel cell described later, in an alkaline direct ethanol fuel cell having a platinum oxide as a catalyst at the anode, platinum oxide is reduced by flowing a reduction current through the anode. You can also. Alternatively, the platinum oxide may be reduced without using electrochemical reduction, such as exposing the anode to a reducing gas. That is, the anode catalyst according to the present invention includes a form obtained by reducing platinum oxide provided in the anode after the fuel cell is manufactured.
白金酸化物を電気化学還元により還元する場合は、その還元電気量（Ｃ）は−０．６以上−０．０５以下が好ましく、−０．４以上−０．０５以下がより好ましく、−０．２以上−０．０５以下がさらに好ましい。還元電気量をこの範囲に制御しつつ白金酸化物に電気化学還元を施すことによって、一層高性能なアノード触媒を得ることができる。 When platinum oxide is reduced by electrochemical reduction, the amount of reduced electricity (C) is preferably −0.6 or more and −0.05 or less, more preferably −0.4 or more and −0.05 or less, and −0 More preferably, it is 2 or more and -0.05 or less. A higher performance anode catalyst can be obtained by subjecting platinum oxide to electrochemical reduction while controlling the amount of reducing electricity within this range.
２．アルカリ直接型エタノール燃料電池用アノード触媒の製造方法
本発明は、アルカリ直接型エタノール燃料電池用アノード触媒の製造方法としての側面も有する。すなわち、白金酸化物を還元する還元工程を備える、アルカリ直接型エタノール燃料電池用アノード触媒の製造方法である。
2. TECHNICAL FIELD The present invention also has an aspect as a method for producing an anode catalyst for an alkaline direct ethanol fuel cell. That is, it is a method for producing an anode catalyst for an alkaline direct ethanol fuel cell, comprising a reduction step for reducing platinum oxide.
還元前後における白金酸化物の組成、形態、さらには還元工程の詳細については上述した通りであり、説明を省略する。尚、上述したように、本発明に係る製造方法は、燃料電池作製後に、アノードに備えられた白金酸化物を還元することでアノード触媒を製造する形態をも含む。もちろん、白金酸化物を還元したうえで担体に担持して（或いは白金酸化物を担体に担持した後、還元処理を施して）アノード触媒を製造してもよく、製造したアノード触媒及びその他燃料電池部品を用いて燃料電池を製造することもできる。 The composition and form of the platinum oxide before and after the reduction and the details of the reduction step are as described above, and the description thereof is omitted. As described above, the manufacturing method according to the present invention includes a mode in which an anode catalyst is manufactured by reducing platinum oxide provided in the anode after the fuel cell is manufactured. Of course, the anode catalyst may be manufactured by reducing the platinum oxide and then supporting it on the carrier (or after carrying the reduction treatment after supporting the platinum oxide on the carrier), and the manufactured anode catalyst and other fuel cells. A fuel cell can also be manufactured using components.
３．アルカリ直接型エタノール燃料電池
本発明は、アルカリ直接型エタノール燃料電池としての側面も有する。すなわち、上述したアノード触媒を備えたアルカリ直接型エタノール燃料電池である。
3. Alkaline direct ethanol fuel cell The present invention also has an aspect as an alkaline direct ethanol fuel cell. That is, an alkaline direct ethanol fuel cell provided with the above-described anode catalyst.
図１に、アルカリ直接型エタノール燃料電池の作動時において生じる電気化学反応を示す。図１に示すように、アルカリ直接型エタノール燃料電池においては、アノード、カソードにおいて、それぞれ以下の電気化学反応が生じる。
（アノード反応）
Ｃ２Ｈ５ＯＨ ＋ １２ＯＨ− → ２ＣＯ２ ＋ ９Ｈ２Ｏ ＋ １２ｅ−
（カソード反応）
３Ｏ２ ＋ ６Ｈ２Ｏ ＋ １２ｅ− → １２ＯＨ−
（全反応）
Ｃ２Ｈ５ＯＨ ＋ ３Ｏ２ → ２ＣＯ２ ＋ ３Ｈ２Ｏ
FIG. 1 shows an electrochemical reaction that occurs during operation of an alkaline direct ethanol fuel cell. As shown in FIG. 1, in an alkaline direct ethanol fuel cell, the following electrochemical reactions occur at the anode and the cathode, respectively.
(Anode reaction)
C 2 H 5 OH + 12OH − → 2CO 2 + 9H 2 O + 12e −
(Cathode reaction)
3O 2 + 6H 2 O + 12e − → 12OH −
(All reactions)
C 2 H 5 OH + 3O 2 → 2CO 2 + 3H 2 O
このような電気化学反応を伴うアルカリ直接型エタノール燃料電池のアノードにおいて、本発明に係るアノード触媒が適用される。本発明に係るアノード触媒は、従来の貴金属系触媒よりもアルカリ条件下におけるエタノール酸化特性が飛躍的に向上しており、燃料電池全体としての出力を従来よりも飛躍的に向上させることが可能である。 The anode catalyst according to the present invention is applied to the anode of an alkaline direct ethanol fuel cell with such an electrochemical reaction. The anode catalyst according to the present invention has drastically improved ethanol oxidation characteristics under alkaline conditions than conventional noble metal catalysts, and can greatly improve the output of the fuel cell as a whole. is there.
アルカリ直接型エタノール燃料電池は、アノードにおいて本発明に係るアノード触媒が採用されていれば、カソード、電解質及びその他燃料電池の構造（燃料供給手段・排出手段、ガス拡散層、筐体等）については特に限定されるものではなく、従来公知のカソード、電解質等を適宜採用できる。尚、電解質としては、ＫＯＨ水溶液等のアルカリ電解液、或いは、水酸化物イオンを伝導可能な高分子電解質膜を用いることができるが、特に、セル構造を簡略化できる観点から、固体高分子電解質膜（いわゆる、アニオン交換膜）を用いることが好ましい。 If the anode catalyst according to the present invention is employed in the anode of an alkaline direct ethanol fuel cell, the structure of the cathode, electrolyte and other fuel cells (fuel supply means / discharge means, gas diffusion layer, casing, etc.) It is not particularly limited, and conventionally known cathodes, electrolytes and the like can be appropriately employed. As the electrolyte, an alkaline electrolyte such as a KOH aqueous solution or a polymer electrolyte membrane capable of conducting hydroxide ions can be used. In particular, from the viewpoint of simplifying the cell structure, a solid polymer electrolyte can be used. It is preferable to use a membrane (so-called anion exchange membrane).
４．アルカリ直接型エタノール燃料電池の出力向上方法
本発明は、アルカリ直接型エタノール燃料電池の出力向上方法としての側面も有する。すなわち、アノードに触媒として白金酸化物を備えるアルカリ直接型エタノール燃料電池において、当該白金酸化物を還元する還元工程を備える、アルカリ直接型エタノール燃料電池の出力向上方法である。
4). TECHNICAL FIELD The present invention also has an aspect as a method for improving the output of an alkaline direct ethanol fuel cell. That is, in an alkaline direct ethanol fuel cell having platinum oxide as a catalyst at the anode, the output improving method of the alkaline direct ethanol fuel cell includes a reduction step of reducing the platinum oxide.
ここで、「アノードに触媒として白金酸化物を備える」とは、燃料電池作製時点（作製直後）においてアノード触媒として白金酸化物を備える形態に限定されない。例えば、アノードに触媒として白金（純金属）を備える燃料電池に対して、白金を意図的に酸化させて白金酸化物としたうえで、その後、白金酸化物を部分的に還元することにより、出力が飛躍的に向上されたアルカリ直接型エタノール燃料電池を得ることもできる。或いは、経年劣化によって白金触媒が酸化することも有り得るが、この場合も還元処理を施すことで、アルカリ直接型エタノール燃料電池の出力を向上させることができる。 Here, “comprising platinum oxide as a catalyst in the anode” is not limited to a mode in which platinum oxide is provided as an anode catalyst at the time of fuel cell production (immediately after production). For example, for a fuel cell with platinum (pure metal) as the catalyst at the anode, the platinum is deliberately oxidized to platinum oxide, and then the platinum oxide is partially reduced for output. It is also possible to obtain an alkaline direct ethanol fuel cell in which the drastic improvement is achieved. Alternatively, the platinum catalyst may be oxidized due to deterioration over time, but in this case as well, the output of the alkaline direct ethanol fuel cell can be improved by performing the reduction treatment.
アルカリ直接型エタノール燃料電池の出力を向上させるに際しても、やはり電気化学還元（電解還元）によって白金酸化物を還元することが好ましい。燃料電池に備えられた電気回路を有効に利用することで、簡便且つ効率的に白金酸化物を還元することができるためである。ただし、アノードを還元ガスに曝す等、電気化学還元によらずとも白金酸化物を還元することも可能ではある。 When improving the output of the alkaline direct ethanol fuel cell, it is also preferable to reduce platinum oxide by electrochemical reduction (electrolytic reduction). This is because platinum oxide can be easily and efficiently reduced by effectively using the electric circuit provided in the fuel cell. However, it is also possible to reduce the platinum oxide without using electrochemical reduction such as exposing the anode to a reducing gas.
以上の通り、本発明によれば、白金酸化物を還元することで、アルカリ条件下におけるエタノール酸化活性が飛躍的に増大されたアノード触媒を得ることができ、当該アノード触媒を用いることでアルカリ直接型エタノール燃料電池の出力を飛躍的に増大させることができる。言い換えれば、従来のアノード触媒（白金−ルテニウム系触媒や白金（純金属）触媒）よりも貴金属使用量を減らしたとしても、十分な出力特性を有するアルカリ直接型エタノール燃料電池を得ることができる。 As described above, according to the present invention, by reducing platinum oxide, it is possible to obtain an anode catalyst whose ethanol oxidation activity under alkaline conditions has been dramatically increased. The output of the type ethanol fuel cell can be dramatically increased. In other words, an alkaline direct ethanol fuel cell having sufficient output characteristics can be obtained even if the amount of noble metal used is reduced as compared with the conventional anode catalyst (platinum-ruthenium catalyst or platinum (pure metal) catalyst).
以下、実施例により、本発明についてさらに詳述するが、本発明は以下の実施例に記載された具体的な形態に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in full detail, this invention is not limited to the specific form described in the following Examples.
＜予備実験＞
図２に示すような装置を用いて、各種触媒薄膜を有するアノード分極について、回転ディスク法によりエタノール酸化特性を評価した。具体的には以下の通りである。
<Preliminary experiment>
Using an apparatus as shown in FIG. 2, the ethanol oxidation characteristics of the anodic polarization having various catalyst thin films were evaluated by the rotating disk method. Specifically, it is as follows.
Ｔｉ基材（Ｔｉ棒）上に電極触媒（白金或いは白金酸化物）をスパッタし、触媒薄膜を有する回転ディスク電極を作製した。作製した電極をエタノール含有アルカリ溶液（１．０Ｍ ＫＯＨ＋０．５Ｍ Ｃ２Ｈ５ＯＨ）又はエタノール非含有アルカリ溶液（１．０Ｍ ＫＯＨ）に浸漬し、下記測定条件にて評価を行った。
作用極：回転ディスク電極
対極：Ｐｔ Ｂｌａｃｋスパイラル
参照極：Ａｇ／ＡｇＣｌ電極
電解液：エタノール含有アルカリ溶液（１．０Ｍ ＫＯＨ＋０．５Ｍ Ｃ２Ｈ５ＯＨ）又はエタノール非含有アルカリ溶液（１．０Ｍ ＫＯＨ）
溶液温度：２９８〜３１３Ｋ
電極回転数：９００ｒｐｍ
掃引範囲：−０．８０〜０．６５Ｖ ｖｓ． ＮＨＥ
掃引速度：５ｍＶ・ｓ−１
An electrode catalyst (platinum or platinum oxide) was sputtered onto a Ti substrate (Ti rod) to produce a rotating disk electrode having a catalyst thin film. The produced electrode was immersed in an ethanol-containing alkaline solution (1.0 M KOH + 0.5 M C 2 H 5 OH) or an ethanol-free alkaline solution (1.0 M KOH), and evaluated under the following measurement conditions.
Working electrode: rotating disk electrode counter electrode: Pt Black spiral reference electrode: Ag / AgCl electrode Electrolyte: ethanol-containing alkaline solution (1.0 M KOH + 0.5 M C 2 H 5 OH) or ethanol-free alkaline solution (1.0 M KOH)
Solution temperature: 298-313K
Electrode rotation speed: 900rpm
Sweep range: -0.80 to 0.65 V vs. NHE
Sweep speed: 5 mV · s −1
予備実験の結果、エタノール非含有溶液でのアノード電流は無視できるほど小さく、アノード電流はエタノールの反応に起因することが分かった。また、触媒をスパッタせずにＴｉ基材のみを用いてアノード電流を測定したところ、無視できるほど小さいものであった。すなわち、Ｔｉ基材上に触媒が存在する場合にのみ、アノード電流が観測できた。 As a result of the preliminary experiment, it was found that the anode current in the ethanol-free solution was negligibly small, and the anode current was caused by the reaction of ethanol. Further, when the anode current was measured using only the Ti base material without sputtering the catalyst, it was negligibly small. That is, the anode current could be observed only when the catalyst was present on the Ti substrate.
以上のことから、触媒をスパッタしたＴｉ基材を、エタノール含有ＫＯＨ溶液中でのアノード分極とすることで、アノード触媒のアルカリ条件下でのエタノール酸化特性を適切に評価できることが分かった。 From the above, it was found that the ethanol oxidation characteristics of the anode catalyst under alkaline conditions can be appropriately evaluated by setting the Ti substrate on which the catalyst is sputtered to anodic polarization in an ethanol-containing KOH solution.
＜実験１＞
（１）Ｔｉ基材上に白金をスパッタしてアノード分極とし、上述した条件でアルカリ溶液中における白金のエタノール酸化特性を評価した。結果を図３に示す。
（２）Ｔｉ基材上に白金酸化物をスパッタしてアノード分極とし、還元電流−０．１Ｃにて電気化学還元したうえで、上述した条件でアルカリ溶液中における白金のエタノール酸化特性を評価した。結果を図３に示す。
<Experiment 1>
(1) Platinum was sputtered onto a Ti base material to form anodic polarization, and the ethanol oxidation characteristics of platinum in an alkaline solution were evaluated under the conditions described above. The results are shown in FIG.
(2) Platinum oxide was sputtered onto a Ti base material to form anodic polarization, electrochemical reduction at a reduction current of -0.1 C, and evaluation of ethanol oxidation characteristics of platinum in an alkaline solution under the conditions described above. . The results are shown in FIG.
図３に示すように、触媒として白金（純金属）を用いた場合よりも、還元した白金酸化物を用いた場合のほうが、アルカリ条件下におけるエタノール酸化活性が８〜９倍大きいことが分かる。すなわち、還元した白金酸化物は、アルカリ直接型エタノール燃料電池のアノード触媒として有用であることが示唆された。 As shown in FIG. 3, it can be seen that the ethanol oxidation activity under alkaline conditions is 8 to 9 times greater when the reduced platinum oxide is used than when platinum (pure metal) is used as the catalyst. That is, it was suggested that the reduced platinum oxide is useful as an anode catalyst for an alkaline direct ethanol fuel cell.
＜実験２＞
（１）Ｔｉ基材上に白金をスパッタしてアノード分極とし、還元電気量を種々変化させて（−０．７〜−０．１Ｃ）電気化学還元したうえで、上述した条件でアルカリ溶液中における白金のエタノール酸化特性を評価した。結果を図４に示す。
（２）Ｔｉ基材上に白金酸化物をスパッタしてアノード分極とし、還元電気量を種々変化させて（−０．７〜−０．１Ｃ）電気化学還元したうえで、上述した条件でアルカリ溶液中における白金のエタノール酸化特性を評価した。結果を図４に示す。
<Experiment 2>
(1) Platinum is sputtered on a Ti base material to form anodic polarization, the amount of reducing electricity is changed variously (-0.7 to -0.1 C), and electrochemically reduced in the above-described conditions in an alkaline solution. The ethanol oxidation characteristics of platinum were evaluated. The results are shown in FIG.
(2) Platinum oxide is sputtered on a Ti base material to form anodic polarization, and the amount of reducing electricity is changed variously (−0.7 to −0.1 C), and then subjected to an electrochemical reduction under the above-described conditions. The ethanol oxidation characteristics of platinum in solution were evaluated. The results are shown in FIG.
図４に示すように、触媒として白金（純金属）を用いた場合は、電気化学還元を施しても、エタノール酸化活性はほとんど変化しないことが分かる。一方、触媒として白金酸化物を用いた場合は、電気化学還元を施すことにより、エタノール酸化活性が急激に増大することが分かる。また、白金酸化物に電気化学還元を施す場合、還元電気量が微小であったとしても十分な触媒活性増大効果が得られることが分かる。還元電気量が大きくし過ぎた場合は、むしろ触媒活性が低下する。本実験によれば、最も好適な還元電気量（Ｃ）は、−０．２以上−０．０５以下であった。 As shown in FIG. 4, it is understood that when platinum (pure metal) is used as the catalyst, the ethanol oxidation activity hardly changes even when electrochemical reduction is performed. On the other hand, when platinum oxide is used as the catalyst, it is understood that the ethanol oxidation activity increases rapidly by performing electrochemical reduction. Further, it is understood that when the platinum oxide is subjected to electrochemical reduction, a sufficient catalytic activity increasing effect can be obtained even if the amount of reducing electricity is very small. If the amount of reducing electricity is too large, the catalytic activity is rather lowered. According to this experiment, the most preferable amount of reducing electricity (C) was -0.2 or more and -0.05 or less.
以上の通り、触媒の還元により得られる触媒活性増大効果は、白金酸化物にのみ特有に見られる効果であることが分かった。 As described above, it was found that the catalytic activity increasing effect obtained by the reduction of the catalyst is an effect that is unique to platinum oxide.
＜実験３＞
上記実験では、触媒を薄膜状とした場合におけるエタノール酸化特性を評価した。しかしながら、実際にアルカリ直接型エタノール燃料電池のアノード触媒として適用することを想定した場合、粉末状態におけるエタノール酸化特性を評価することが好ましい。そこで、粉末状白金（純金属）触媒（Ｐｔ Ｂｌａｃｋ）、未還元の粉末状白金酸化物触媒（Ｐｔ−Ｏｘｉｄｅ Ｂｌａｃｋ）、還元した粉末状白金酸化物触媒（還元電流−０．１５Ｃ）又は粉末状白金−ルテニウム触媒（Ｐｔ−Ｒｕ Ｂｌａｃｋ）のいずれかと、アニオン交換樹脂溶液とを別々にグラッシーカーボン上に担持してアノード電極を作製し、それぞれのアノード電極について、アルカリ条件下におけるエタノール酸化特性を評価した。評価結果を図５、６に示す。
<Experiment 3>
In the above experiment, the ethanol oxidation characteristics were evaluated when the catalyst was in the form of a thin film. However, when actually applied as an anode catalyst of an alkaline direct ethanol fuel cell, it is preferable to evaluate ethanol oxidation characteristics in a powder state. Therefore, powdered platinum (pure metal) catalyst (Pt Black), unreduced powdered platinum oxide catalyst (Pt-Oxide Black), reduced powdered platinum oxide catalyst (reduction current -0.15C) or powdered An anode electrode was prepared by separately supporting one of a platinum-ruthenium catalyst (Pt-Ru Black) and an anion exchange resin solution on glassy carbon, and the ethanol oxidation characteristics under alkaline conditions were evaluated for each anode electrode. did. The evaluation results are shown in FIGS.
尚、本実験においては、白金（純金属）触媒に含まれる白金質量と白金酸化物触媒に含まれる白金質量とを同一とした。また、白金（純金属）触媒と白金−ルテニウム触媒とを同一質量とした（白金−ルテニウム触媒中の白金量が白金（純金属）触媒における白金量よりも少ないものとした）。
すなわち、本実験において、触媒中の白金質量は、白金酸化物触媒＝白金（純金属）触媒＞白金−ルテニウム触媒となる。
In this experiment, the platinum mass contained in the platinum (pure metal) catalyst and the platinum mass contained in the platinum oxide catalyst were the same. Further, the platinum (pure metal) catalyst and the platinum-ruthenium catalyst were made to have the same mass (the platinum amount in the platinum-ruthenium catalyst was less than the platinum amount in the platinum (pure metal) catalyst).
That is, in this experiment, the platinum mass in the catalyst is platinum oxide catalyst = platinum (pure metal) catalyst> platinum-ruthenium catalyst.
図５、６に示すように、白金−ルテニウム触媒は白金（純金属）触媒に比べてエタノール酸化活性が小さい。触媒中の白金量が減少したことにより、触媒活性が低下したと考えられる。すなわち、この結果のみからは、純金属系触媒或いは合金系触媒についてのアルカリ条件下におけるエタノール酸化活性は、触媒に含まれる白金量で議論できるようにも見える。
しかしながら、白金酸化物触媒と白金（純金属）触媒とについては、この議論は成り立たない。図５、６に示すように、白金（純金属）触媒と、同一量の白金を含む白金酸化物触媒とを比較すると、未還元の白金酸化物触媒は白金（純金属）触媒よりもエタノール酸化活性が小さいが、還元後の白金酸化物触媒は白金（純金属）触媒を大きく上回るエタノール酸化活性を有することが分かる。
As shown in FIGS. 5 and 6, the platinum-ruthenium catalyst has a smaller ethanol oxidation activity than the platinum (pure metal) catalyst. It is considered that the catalytic activity was lowered due to the decrease in the amount of platinum in the catalyst. That is, from this result alone, it appears that the ethanol oxidation activity of the pure metal catalyst or alloy catalyst under alkaline conditions can be discussed by the amount of platinum contained in the catalyst.
However, this discussion does not hold for platinum oxide catalysts and platinum (pure metal) catalysts. As shown in FIGS. 5 and 6, when a platinum (pure metal) catalyst is compared with a platinum oxide catalyst containing the same amount of platinum, the unreduced platinum oxide catalyst is more ethanol-oxidized than the platinum (pure metal) catalyst. Although the activity is small, it can be seen that the platinum oxide catalyst after reduction has an ethanol oxidation activity far exceeding that of the platinum (pure metal) catalyst.
以上のことから、アルカリ直接型エタノール燃料電池においては、白金酸化物を還元してなるアノード触媒を用いることで、使用する貴金属量を削減しつつも、出力を飛躍的に増大させることが可能なことが分かった。 From the above, in the alkaline direct ethanol fuel cell, it is possible to dramatically increase the output while reducing the amount of noble metal used by using the anode catalyst formed by reducing platinum oxide. I understood that.
以上、現時点において、最も実践的であり、且つ、好ましいと思われる実施形態に関連して本発明を説明したが、本発明は、本願明細書中に開示された実施形態に限定されるものではなく、請求の範囲及び明細書全体から読み取れる発明の要旨あるいは思想に反しない範囲で適宜変更可能であり、そのような変更を伴うアルカリ直接型エタノール燃料電池用アノード触媒及び該触媒を備えたアルカリ直接型エタノール燃料電池、該触媒の製造方法、並びに、アルカリ直接型エタノール燃料電池の出力向上方法もまた本発明の技術範囲に包含されるものとして理解されなければならない。 Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the invention is not limited to the embodiments disclosed herein. The anode catalyst for an alkaline direct ethanol fuel cell and the alkali direct equipped with the catalyst can be appropriately changed without departing from the gist or concept of the invention that can be read from the claims and the entire specification. A type ethanol fuel cell, a method for producing the catalyst, and a method for improving the output of an alkaline direct type ethanol fuel cell should also be understood as being included in the technical scope of the present invention.
本発明はアルカリ直接型エタノール燃料電池用のアノード触媒として利用可能である。また、白金系アノード触媒を備えるアルカリ直接型エタノール燃料電池について、その出力を向上させる方法としても利用可能である。 The present invention can be used as an anode catalyst for an alkaline direct ethanol fuel cell. Further, the present invention can also be used as a method for improving the output of an alkaline direct ethanol fuel cell equipped with a platinum-based anode catalyst.
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