WO2004019436A1 - Pile a combustible du type a polymere solide - Google Patents

Pile a combustible du type a polymere solide Download PDF

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Publication number
WO2004019436A1
WO2004019436A1 PCT/JP2003/010478 JP0310478W WO2004019436A1 WO 2004019436 A1 WO2004019436 A1 WO 2004019436A1 JP 0310478 W JP0310478 W JP 0310478W WO 2004019436 A1 WO2004019436 A1 WO 2004019436A1
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WO
WIPO (PCT)
Prior art keywords
acid
fuel cell
fuel
polymer electrolyte
catalyst
Prior art date
Application number
PCT/JP2003/010478
Other languages
English (en)
Japanese (ja)
Inventor
Naoko Fujiwara
Kazuaki Yasuda
Yoshinori Miyazaki
Tetsuhiko Kobayashi
Original Assignee
National Institute Of Advanced Industrial Science And Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Institute Of Advanced Industrial Science And Technology filed Critical National Institute Of Advanced Industrial Science And Technology
Priority to AU2003257581A priority Critical patent/AU2003257581A1/en
Priority to JP2004530570A priority patent/JP4238364B2/ja
Publication of WO2004019436A1 publication Critical patent/WO2004019436A1/fr

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Classifications

    • 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
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • 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
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • H01M8/222—Fuel cells in which the fuel is based on compounds containing nitrogen, e.g. hydrazine, ammonia
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a polymer electrolyte fuel cell.
  • Polymer electrolyte fuel cells can be used for power supplies for electric vehicles, aerospace equipment, and other transport equipment, and for portable use, because of their high current density at low temperatures and the possibility of miniaturization. Research and development are progressing as power sources.
  • As the fuel supplied to the polymer electrolyte fuel cell natural gas, hydrogen gas produced by reforming methanol, gasoline, or the like is generally used.
  • polymer electrolyte fuel cells that directly supply methanol as fuel have attracted attention in recent years because of their convenience as liquid fuels for storage and transportation.
  • direct current fuel cells are the mainstream for small power supplies and chargers for mobile devices.
  • wearable information terminals, implantable biosensors, and medical devices are also being developed, and these microelectronic devices can be powered only by supplying fuel without charging them.
  • the application of time-operated direct fuel cells is being considered.
  • the direct methanol fuel cell has a structure in which electrodes are attached to both sides of a solid polymer electrolyte membrane, similarly to a solid polymer fuel cell using pure hydrogen or reformed hydrogen as a fuel.
  • a platinum-ruthenium catalyst is used for the anode (fuel electrode)
  • a platinum catalyst is used for the power source (air electrode).
  • the present inventor has been studying a polymer electrolyte direct fuel cell that supplies another compound as a fuel instead of methanol while paying attention to the problems of the conventional technology.
  • a group of compounds such as ascorbic acid, which is used as a reducing agent in a reaction process such as catalyst preparation, synthesis reaction, and electroless plating, is used as a fuel, solids that can reduce the problems of the prior art
  • a polymer type direct fuel cell can be obtained.
  • the present invention provides the following polymer electrolyte direct fuel cell.
  • At least one member selected from the group consisting of ascorbic acid, isoascorbic acid, sulfurous acid, bisulfite, dithionous acid and salts thereof is used as a fuel, and a current collector composed of a power pad or carbon cloth is used as a solid.
  • the direct fuel cell of the present invention comprises a solution of a compound selected from ascorbic acid, isoascorbic acid, citric acid, tartaric acid, sulfurous acid, thiosulfuric acid, hydrogensulfite, dithionous acid, phosphorous acid, hypophosphorous acid, and salts thereof. Is supplied as fuel to generate electricity.
  • Fig. 1 shows cyclic poles measured in a 0.5 M sulfuric acid solution on a platinum-ruthenium electrode using ascorbic acid, sodium sulfite, sodium bisulfite, sodium dithionite and hypophosphorous acid, respectively. Evening gram. Figure 1 also shows the results for methanol for comparison.
  • ascorbic acid, isoascorbic acid, citric acid, tartaric acid and their salts sodium, potassium, magnesium, calcium
  • ascorbic acid, isoascorbic acid, citric acid, tartaric acid and their salts are used as fuel, only the C-OH is oxidized to a ketone group and no dangerous compounds are produced.
  • sulfurous acid, thiosulfuric acid, hydrogen sulfite, dithionous acid, phosphorous acid, hypophosphorous acid and their salts are corrosive and irritating. Although it is known to have properties and requires careful handling, it is not a designated compound such as methanol.
  • Sulfurous acid, hydrogen sulfite, thiosulfuric acid, dithionous acid and their salts may produce sulfuric acid, and phosphorous acid, hypophosphorous acid and their salts may produce phosphoric acid. By collecting in the reservoir, release to the outside of the device can be prevented, so that practical problems can be avoided.
  • a known polymer electrolyte membrane, an electrode catalyst, a membrane-electrode assembly, and a cell structure used in an ordinary polymer electrolyte fuel cell can be applied to the fuel cell according to the present invention.
  • electrode catalyst various kinds of conventionally known metals and metal alloys can be used as the electrode catalyst.
  • Various types of metal catalysts, or supported catalysts in which fine particles of these catalysts are dispersed on a carrier such as carbon can be used.
  • a carbon such as carbon black can be used without using a noble metal.
  • the material can be used as it is as the anode electrode.
  • carbon black having a high specific surface area (50 m 2 / g or more) is more preferable.
  • a current collector such as carbon paper or carbon cloth is used as a solid.
  • polymer electrolyte membrane various ion-exchange resin membranes such as perfluorocarbon-based, styrene-dipinylbenzene-based copolymer, and polybenzimidazole-based can be used.
  • a joined body of the solid polymer electrolyte membrane and the electrode catalyst is produced in the same manner as a generally known joined body.
  • a method is used in which a catalyst ink prepared by mixing a catalyst powder and an electrolyte solution is thinned and then hot-pressed on the electrolyte membrane or directly coated on the polymer membrane and dried.
  • a catalyst can be directly attached to the solid polymer membrane by a method such as adsorption reduction, electroless plating, sputtering, or CVD.
  • electrodes are fabricated by applying a catalyst ink directly to a gas diffusion layer such as a carbon vapor or a carbon cloth or a current collector and drying it, or impregnating and reducing a metal complex as a precursor. May be.
  • a carbon material such as carbon black can be used as the anode catalyst.
  • the current collector itself made of carbon paper, carbon cloth, or the like can also function as an anode catalyst.
  • Both sides of the obtained membrane-electrode assembly are made of carbon paper or carbon cloth T / JP2003 / 010478
  • At least one of the above compounds is supplied as a fuel to the anode side in the form of a solution of about 10 to 5 M (more preferably, about 10 to 3 M), and air or oxygen is supplied to the power source side. Disperse naturally.
  • the operating temperature of the fuel cell of the present invention varies depending on the electrolyte membrane used, but is usually about 0 to 150 ° C, more preferably about 10 to 100 ° C.
  • the direct fuel cell which uses the compound instead of methanol designated as a deleterious substance as a fuel of a polymer electrolyte fuel cell is obtained.
  • each compound used in the present invention does not generate harmful substances such as formaldehyde and formic acid as oxidation products.
  • the direct fuel cell according to the present invention can reduce the crossover that degrades the performance of the direct methanol fuel cell.
  • some of the compounds used in the present invention can realize a high-performance polymer electrolyte fuel cell even when a carbon material is used as a catalyst on the anode side instead of an expensive noble metal. .
  • the effect is remarkable when a power pump rack having a large specific surface area is used as an anode catalyst.
  • FIG. 1 is a cyclic portogram of each fuel used in the present invention in a 0.5 M sulfuric acid solution.
  • FIG. 2 is a graph showing current-voltage characteristics of the fuel cell according to Example 1.
  • FIG. 3 is a graph showing current-voltage characteristics of the fuel cell according to Example 2.
  • FIG. 4 is a graph showing the cathode potentials of the fuel cells according to Example 3 and Comparative Example 2.
  • FIG. 5 is a graph showing current-voltage characteristics of the fuel cell according to Example 4.
  • FIG. 6 is a graph showing a current-voltage characteristic of the fuel cell according to the fifth embodiment.
  • FIG. 7 is a graph showing current-voltage characteristics of the fuel cell according to Example 6.
  • FIG. 8 is a graph showing current-voltage characteristics of the fuel cell according to Embodiment 7.
  • FIG. 9 is a graph showing current-voltage characteristics of the fuel cell according to Example 8.
  • FIG. 10 is a graph showing current-voltage characteristics of the fuel cell according to Embodiment 9.
  • FIG. 11 is a graph showing current-voltage characteristics of the fuel cell according to Example 10;
  • Example 1 Example 1
  • Platinum-ruthenium black was used as the anode catalyst, and platinum black treated with water repellency with polytetrafluoroethylene was used as the power sword catalyst.
  • Each catalyst was mixed with a polymer electrolyte solution to form a catalyst ink, and a thin film was formed to form an electrode sheet. Then, hot pressing was performed on both sides of a polymer electrolyte membrane (trade name of “Nafion-117”, manufactured by DuPont). Thus, a membrane-electrode assembly was obtained.
  • a fuel cell is assembled by sandwiching both sides of the obtained membrane-electrode assembly with a force cloth, an aqueous solution of a predetermined fuel is supplied to the anode, and air is naturally diffused to the force sword, thereby at room temperature.
  • the power generation performance of the fuel cell was evaluated.
  • Table 1 shows the values of the open circuit voltage when using various fuels.
  • Fig. 2 shows the current-voltage characteristics when ascorbic acid, sodium dithionite, phosphorous acid, and hypophosphorous acid each having an aqueous solution concentration of 0.5M were used as fuel.
  • Example 2 Fuel cells were produced in the same manner as in Example 1, except that platinum, ruthenium, palladium, iridium, and rhodium were used as anode catalysts instead of platinum-ruthenium black in Example 1.
  • a fuel cell was manufactured according to Example 1 by directly contacting the carbon cloth with the polymer electrolyte membrane without using a catalyst on the anode side.
  • FIG. 3 shows the current-voltage characteristics of these fuel cells.
  • FIG. 3 also shows the current-voltage characteristics of the cell using ascorbic acid as a fuel according to the first embodiment.
  • Fig. 3 shows that the oxidation reaction of ascorbic acid proceeded on all anodes, including the case where no catalyst was used for the anodes, and the fuel cell was operated.
  • the types of anode catalysts that can be used are increased, and even if a platinum-ruthenium catalyst is not used on the anode side, or even if a catalyst is not used, the fuel cell can be used. It is clear that power generation is possible.
  • a 1 M methanol solution was supplied to the anode side of the fuel cell prepared in Example 2, and the power generation performance was evaluated.
  • a 1 M methanol solution was placed on the anode side of the fuel cell fabricated in the same manner as in Example 3. The solution was supplied and the force sword potential was measured at room temperature.
  • Example 3 using ascorbic acid as a fuel according to the present invention shows a higher force sword potential than Comparative Example 2 using methanol as a fuel. It is known that methanol has a large membrane permeability from the anode to the force sword, and the cathodic potential decreases as a hybrid potential. On the other hand, the crossover is considered to be small in the fuel used in the present invention since the force sword potential is high.
  • Fuel cells were fabricated in the same manner as in Example 1 using various blacks of platinum, ruthenium, palladium, iridium, rhodium and platinum-ruthenium as anode catalysts.
  • Example 1 a fuel cell was fabricated according to Example 1 by directly contacting a carbon cloth as a current collector with the polymer electrolyte membrane without using a catalyst on the anode side.
  • Fuel cells were fabricated in the same manner as in Example 1 using various blacks of platinum, ruthenium, palladium, iridium, rhodium and platinum-ruthenium as anode catalysts.
  • a fuel cell was manufactured according to Example 1. Next, a 0.05 M aqueous solution of sulfurous acid was supplied to the anode, and air was spontaneously diffused into the power sword to evaluate the power generation characteristics of each fuel cell at room temperature.
  • Figure 6 shows the current-voltage characteristics of these fuel cells.
  • Example 1 without using platinum-ruthenium black used as an anode catalyst, only one side of the polymer electrolyte membrane was hot-pressed with platinum black as a force sword to form did. Then, a carbon cloth attached with carbon black by the above-described method is applied to the film surface on the opposite side of the force sode of the obtained membrane one-sided force bonded body, and a normal carbon cloth is pressed to the cathode side film surface, and the fuel cell is pressed. The cell was assembled.
  • FIG. 11 shows current-voltage characteristics of these fuel cells.
  • FIG. 11 shows only the carbon cloth (force
  • Fig. 11 shows that the performance of the ascorbic acid fuel cell is improved by attaching various carbon blacks with a large specific surface area to the carbon cloth arranged on the anode side.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne une pile à combustible directe du type à polymère solide, qui se caractérise en ce qu'au moins un composé sélectionné dans le groupe constitué par un acide ascorbique, un acide iso-ascorbique, un acide citrique, un acide tartarique, un acide sulfurique, un acide thiosulfurique, un acide hydrogène sulfureux, un acide dithionique, un acide phosphorique, un acide phosphinique, ou des sels dudit composé, est utilisé directement comme combustible.
PCT/JP2003/010478 2002-08-21 2003-08-20 Pile a combustible du type a polymere solide WO2004019436A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003257581A AU2003257581A1 (en) 2002-08-21 2003-08-20 Solid polymer type fuel cell
JP2004530570A JP4238364B2 (ja) 2002-08-21 2003-08-20 固体高分子形燃料電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002240086 2002-08-21
JP2002-240086 2002-08-21

Publications (1)

Publication Number Publication Date
WO2004019436A1 true WO2004019436A1 (fr) 2004-03-04

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100388553C (zh) * 2005-09-28 2008-05-14 浙江大学 微型生物燃料电池及其制造方法
JP2011060531A (ja) * 2009-09-09 2011-03-24 National Institute Of Advanced Industrial Science & Technology 直接型燃料電池
WO2014098171A1 (fr) * 2012-12-20 2014-06-26 トヨタ自動車株式会社 Pile à combustible
JP2016096156A (ja) * 2005-02-11 2016-05-26 ダブリュ．エル．ゴア アンド アソシエイツ，インコーポレイティドＷ．Ｌ． Ｇｏｒｅ ＆ Ａｓｓｏｃｉａｔｅｓ， Ｉｎｃｏｒｐｏｒａｔｅｄ 燃料電池の劣化を低減する方法
CN109952677A (zh) * 2016-08-05 2019-06-28 罗地亚经营管理公司 无膜直接型燃料电池
JP2020053261A (ja) * 2018-09-27 2020-04-02 東洋インキＳｃホールディングス株式会社 燃料電池正極用触媒、燃料電池正極用ペースト組成物、燃料電池用正極、燃料電池、および水分センサー
JP2020098725A (ja) * 2018-12-18 2020-06-25 東洋インキＳｃホールディングス株式会社 バイオ燃料電池アノード用触媒インキ材料、バイオ燃料電池アノード用触媒インキ組成物、バイオ燃料電池アノード、バイオ燃料電池デバイス

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002151132A (ja) * 2000-11-07 2002-05-24 Japan Storage Battery Co Ltd グリコールを燃料にした燃料電池

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002151132A (ja) * 2000-11-07 2002-05-24 Japan Storage Battery Co Ltd グリコールを燃料にした燃料電池

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Sangyo gijutsu sogo ken seikatsu kenkyokei", THE ELECTROCHEMICAL SOCIETY OF JAPAN TAIKAI KOEN YOSHISHU, vol. 70, 25 March 2003 (2003-03-25), pages 299, XP002974990 *
"Sangyo hijutsu sougo ken seikatsu kankyokei", DENKI KAGAKU SHUKI TAIKAI KOEN YOSHISHU, vol. 2002, 5 September 2002 (2002-09-05), pages 92, XP002974989 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016096156A (ja) * 2005-02-11 2016-05-26 ダブリュ．エル．ゴア アンド アソシエイツ，インコーポレイティドＷ．Ｌ． Ｇｏｒｅ ＆ Ａｓｓｏｃｉａｔｅｓ， Ｉｎｃｏｒｐｏｒａｔｅｄ 燃料電池の劣化を低減する方法
CN100388553C (zh) * 2005-09-28 2008-05-14 浙江大学 微型生物燃料电池及其制造方法
JP2011060531A (ja) * 2009-09-09 2011-03-24 National Institute Of Advanced Industrial Science & Technology 直接型燃料電池
WO2014098171A1 (fr) * 2012-12-20 2014-06-26 トヨタ自動車株式会社 Pile à combustible
CN104854748A (zh) * 2012-12-20 2015-08-19 丰田自动车株式会社 燃料电池
JP5888438B2 (ja) * 2012-12-20 2016-03-22 トヨタ自動車株式会社 燃料電池
US9742020B2 (en) 2012-12-20 2017-08-22 Toyota Jidosha Kabushiki Kaisha Fuel cell
CN109952677A (zh) * 2016-08-05 2019-06-28 罗地亚经营管理公司 无膜直接型燃料电池
JP2020053261A (ja) * 2018-09-27 2020-04-02 東洋インキＳｃホールディングス株式会社 燃料電池正極用触媒、燃料電池正極用ペースト組成物、燃料電池用正極、燃料電池、および水分センサー
JP7155814B2 (ja) 2018-09-27 2022-10-19 東洋インキＳｃホールディングス株式会社 燃料電池正極用触媒、燃料電池正極用ペースト組成物、燃料電池用正極、燃料電池、および水分センサー
JP2020098725A (ja) * 2018-12-18 2020-06-25 東洋インキＳｃホールディングス株式会社 バイオ燃料電池アノード用触媒インキ材料、バイオ燃料電池アノード用触媒インキ組成物、バイオ燃料電池アノード、バイオ燃料電池デバイス
JP7205209B2 (ja) 2018-12-18 2023-01-17 東洋インキＳｃホールディングス株式会社 バイオ燃料電池アノード用触媒インキ材料、バイオ燃料電池アノード用触媒インキ組成物、バイオ燃料電池アノード、バイオ燃料電池デバイス

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AU2003257581A1 (en) 2004-03-11
JPWO2004019436A1 (ja) 2005-12-15
JP4238364B2 (ja) 2009-03-18

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