WO2013005814A1 - Batterie au biocarburant - Google Patents

Batterie au biocarburant Download PDF

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Publication number
WO2013005814A1
WO2013005814A1 PCT/JP2012/067250 JP2012067250W WO2013005814A1 WO 2013005814 A1 WO2013005814 A1 WO 2013005814A1 JP 2012067250 W JP2012067250 W JP 2012067250W WO 2013005814 A1 WO2013005814 A1 WO 2013005814A1
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WIPO (PCT)
Prior art keywords
fuel
biofuel cell
power generation
anode
cell according
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PCT/JP2012/067250
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English (en)
Japanese (ja)
Inventor
洋樹 三田
修二 藤田
貴晶 中川
酒井　秀樹
村田　賢一
隆平 松本
戸木田　裕一
Original Assignee
ソニー株式会社
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Priority claimed from JP2011149854A external-priority patent/JP2013016413A/ja
Priority claimed from JP2011169024A external-priority patent/JP2013033630A/ja
Application filed by ソニー株式会社 filed Critical ソニー株式会社
Publication of WO2013005814A1 publication Critical patent/WO2013005814A1/fr

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    • 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
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of 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
    • 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

  • This technology relates to a biofuel cell using oxidoreductase.
  • it is related with the fuel supply technique in a biofuel cell.
  • the present invention relates to a biofuel cell in which an oxidoreductase is present on the electrode surface.
  • FIG. 15 is a diagram schematically showing the power generation principle of a biofuel cell using an enzyme. For example, in the case of a biofuel cell using glucose as a fuel as shown in FIG.
  • the negative electrode (anode) 101 decomposes glucose (Glucose) with an enzyme immobilized on the surface and takes out electrons (e ⁇ ). Proton (H + ) is generated.
  • protons (H + ) transported from the negative electrode (anode) 101 through the proton conductor 103 electrons (e ⁇ ) sent through an external circuit, and air, for example, Water (H 2 O) is produced by oxygen (O 2 ) in the medium.
  • the reaction of these positive / negative electrodes occurs simultaneously, and an electrical energy generate
  • the direct methanol type fuel cell has a problem that the voltage of a single cell is low.
  • the conventional fuel cell is generally used in the form of a module in which a plurality of cells are connected in series (see, for example, Patent Documents 1 and 2).
  • a biofuel cell has also been proposed with a structure in which a plurality of cells are connected in parallel and / or in series for the purpose of improving output (see, for example, Patent Documents 3 and 4).
  • the fuel cell can generate power continuously over a long period of time by additionally supplying fuel.
  • the amount of the fuel solution itself does not decrease greatly, so it is difficult to visually determine the fuel consumption.
  • the conventional fuel cell described above has the following problems.
  • a fuel cell can generate power continuously over a long period of time by supplying additional fuel.
  • a fuel inlet is provided for each cell. It must be provided and supplied separately. For this reason, the conventional fuel cell has a problem that the work at the time of fuel supply is complicated. Even if only one fuel inlet is used, a fuel distribution mechanism such as a flow path must be provided inside the battery, resulting in a complicated device and a reduction in output per unit volume.
  • a plurality of fuel electrodes are immersed in a common fuel tank.
  • the fuel solution also serves as a proton conductor.
  • the structure cannot be adopted.
  • the fuel solution is independent for each cell and needs to be in a non-contact state.
  • the main object of the present disclosure is to provide a biofuel cell that can supply fuel to a plurality of cells connected in series.
  • the method described in Patent Document 5 described above requires that a resistance measuring device be separately provided in the cell. Providing such a resistance measuring device or a detector such as a remaining fuel detection sensor requires power to operate the detector and complicates the device configuration.
  • a biofuel cell includes two or more power generation units connected in series, an electrode having an oxidoreductase on the surface, a fuel supply unit communicating with a fuel inlet of each power generation unit, and the fuel And a lid that closes the supply section and each fuel inlet.
  • the power generation units can be separated from each other by a partition plate, and a concave fuel supply unit can be formed by providing a part of the partition plate with a low height.
  • the lid may be provided with a filling amount adjusting unit for adjusting the amount of fuel filled in each power generation unit.
  • one or two or more pressing members for pressing each electrode from the inside may be arranged in the fuel tank of the power generation unit.
  • the pressing member may have a structure in which a plurality of rod-shaped members extending in the width direction and the height direction are integrated.
  • the biofuel cell according to the present disclosure includes a power generation unit including an electrode having a surface on which an oxidoreductase is present, a detection unit that detects a change in pH of the fuel solution by a color change, and a housing in which the power generation unit is accommodated.
  • a container, and at least a position where the detection unit is visible is transparent or translucent.
  • a pH test paper may be disposed in the fuel solution as the detection unit. In that case, the pH test paper can be placed near the anode.
  • a pH indicator may be added to the fuel solution.
  • the container can be transparent or translucent at a position where the vicinity of the anode can be seen.
  • the fuel supply unit communicating with the fuel injection port of each power generation unit since the fuel supply unit communicating with the fuel injection port of each power generation unit is provided, fuel can be supplied to a plurality of cells connected in series by a single operation. According to the present disclosure, since the pH change of the fuel solution can be visually confirmed, it is possible to easily determine the deterioration of the cell performance due to the fuel consumption.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of the biofuel cell according to the first embodiment of the present disclosure.
  • FIG. 2 is a cross-sectional view schematically showing a state where the fuel cell main body 2 and the lid 3 are separated from each other in the biofuel cell 1 shown in FIG.
  • FIG. 3 is an exploded perspective view schematically showing the configuration of the power generation unit 11 of the biofuel cell 1 shown in FIG. 4 (a) and 4 (b) are plan views showing examples of arrangement of the pressing member 28, and
  • FIG. 4 (c) is a plan view showing a conventional battery structure without the pressing member.
  • FIG. 5 is a graph showing the results of constant potential measurements on the biofuel cells of FIGS.
  • FIG. 6 is an exploded perspective view schematically showing another configuration of the power generation unit 11 of the biofuel cell 1 shown in FIG.
  • FIG. 7 is a graph showing a change in output depending on the presence or absence of the press bar 48, with time on the horizontal axis and current value on the vertical axis.
  • FIG. 8 is a perspective view schematically showing a method of supplying a fuel solution to the biofuel cell 1 shown in FIG.
  • FIG. 9 is a cross-sectional view schematically illustrating a configuration of a biofuel cell according to a first modified example of the first embodiment of the present disclosure.
  • FIG. 10 is a perspective view illustrating a configuration of a biofuel cell according to a second modification example of the first embodiment of the present disclosure.
  • FIG. 11 is an exploded perspective view schematically illustrating the configuration of the power generation unit of the biofuel cell according to the first embodiment of the present disclosure.
  • FIG. 12 is an exploded perspective view schematically illustrating a configuration of a biofuel cell according to a modification of the first and second embodiments of the present disclosure.
  • FIG. 13 is a diagram illustrating a configuration example of a storage container that stores the biofuel cell illustrated in FIG. 12.
  • FIG. 14 is a diagram illustrating another configuration example of the storage container that stores the biofuel cell illustrated in FIG. 12.
  • FIG. 15 is a diagram schematically showing the power generation principle of a biofuel cell using an enzyme.
  • First embodiment Example of a biofuel cell provided with a fuel supply unit common to a plurality of fuel units
  • First modification of the first embodiment (An example of a biofuel cell in which a fuel solution amount adjustment hole is provided in the lid) 3.
  • Second modification of the first embodiment (An example of a biofuel cell in which a fuel solution amount adjustment hole is provided on the side of the housing) 4).
  • Second embodiment (Example of placing pH test paper) 5.
  • Third embodiment Example of adding pH indicator to fuel solution
  • Modified example Example of rotating battery) ⁇ 1.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of the biofuel cell of this embodiment
  • FIG. 2 is a cross-sectional view schematically showing a state where the fuel cell main body and the lid are separated.
  • the biofuel cell 1 of the present embodiment closes at least the fuel cell main body 2 composed of stacked cells in which a plurality of power generation units 11 are connected in series and the fuel supply unit 14. And a lid 3.
  • Each power generation unit 11 of the fuel cell main body 2 is electrically insulated by a partition plate 12.
  • FIG. 3 is an exploded perspective view schematically showing the configuration of the power generation unit 11 of the biofuel cell 1 shown in FIG.
  • each power generation unit 11 is provided with an anode 21 and a cathode 22, and a separator 24 is disposed between them. Further, current collectors 23 and 25 are arranged in contact with the anode 21 and the cathode 22, respectively.
  • a fuel tank 27 is disposed between the separator 24 and the anode 21, and the fuel solution 4 stored in the fuel tank 27 comes into contact with the anode 21.
  • one or more pressing members 28 can be arranged.
  • an oxidoreductase is present on the electrode surface of the anode 21 or the cathode 22 or both.
  • the surface of the electrode includes the entire outer surface of the electrode and the inner surface of the void inside the electrode, and the same applies to the following description.
  • the anode 21 is a fuel electrode.
  • an anode 21 having an oxidoreductase immobilized on the surface of an electrode made of a conductive porous material can be used.
  • the conductive porous material used in this case known materials can be used, and in particular, carbon-based materials such as porous carbon, carbon pellets, carbon felt, carbon paper, carbon fiber, or a laminate of carbon fine particles. Material is preferred.
  • the enzyme immobilized on the surface of the anode 21 for example, when the fuel component is glucose, glucose dehydrogenase (GDH) that decomposes glucose can be used.
  • GDH glucose dehydrogenase
  • a monosaccharide such as glucose
  • a coenzyme oxidase and an electron mediator are immobilized on the anode surface together with an oxidase that promotes and decomposes monosaccharide such as GDH.
  • a coenzyme oxidase is a coenzyme that is reduced by an oxidase (eg, NAD + , NADP + Etc.) and a reduced form of a coenzyme (for example, NADH, NADPH, etc.), such as diaphorase.
  • an oxidase eg, NAD + , NADP + Etc.
  • a reduced form of a coenzyme for example, NADH, NADPH, etc.
  • the electron mediator a compound having a quinone skeleton is preferably used, and a compound having a naphthoquinone skeleton is particularly preferable.
  • 2-amino-1,4-naphthoquinone ANQ
  • 2-amino-3-methyl-1,4-naphthoquinone ANQ
  • 2-methyl-1,4-naphthoquinone VK3
  • 2- Amino-3-carboxy-1,4-naphthoquinone ACNQ
  • the compound having a quinone skeleton for example, a compound having an anthraquinone skeleton such as anthraquinone-1-sulfonic acid, anthraquinone-2-sulfonic acid and anthraquinone-2-carboxylic acid, and derivatives thereof Can also be used. Furthermore, you may fix
  • polysaccharide refers to a polysaccharide in a broad sense and refers to all carbohydrates that produce two or more monosaccharides by hydrolysis, and includes oligosaccharides such as disaccharides, trisaccharides, and tetrasaccharides.
  • starch amylose, amylopectin, glycogen, cellulose, maltose, sucrose, and lactose. These are a combination of two or more monosaccharides, and any polysaccharide contains glucose as a monosaccharide of the binding unit.
  • Amylose and amylopectin are components contained in starch, and starch is a mixture of amylose and amylopectin.
  • glucoamylase is used as a polysaccharide degrading enzyme and glucose dehydrogenase is used as an oxidase degrading monosaccharide
  • a polysaccharide that can be decomposed into glucose by glucoamylase is used as the fuel component. can do.
  • polysaccharides examples include starch, amylose, amylopectin, glycogen and maltose.
  • glucoamylase is a degrading enzyme that hydrolyzes ⁇ -glucan such as starch to produce glucose
  • glucose dehydrogenase is an oxidase that oxidizes ⁇ -D-glucose to D-glucono- ⁇ -lactone.
  • the anode 2 is not limited to the one having the oxidoreductase immobilized on the surface. For example, if the oxidoreductase is present on the electrode surface, the anode 2 has an oxidoreductase, for example.
  • the cathode 22 is an air electrode and is in contact with the gas phase (air) through the gas-liquid separation membrane 26.
  • the electrode constituting the cathode 22 is not particularly limited.
  • an electrode in which an oxidoreductase and an electron mediator are immobilized on the surface of an electrode made of a conductive porous material can be used.
  • the conductive porous material forming the cathode 22 known materials can be used, and in particular, carbon-based materials such as porous carbon, carbon pellets, carbon felt, carbon paper, carbon fiber or carbon fine particle laminates. Material is preferred.
  • Examples of the oxygen reductase immobilized on the cathode 22 include bilirubin oxidase, laccase, and ascorbate oxidase.
  • Examples of the electron mediator immobilized together with these enzymes include potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), and potassium octacyanotungstate.
  • the cathode 22 is not limited to the one having the oxidoreductase immobilized on the surface. For example, if the oxidoreductase is present on the electrode surface, the cathode 22 has, for example, an oxidoreductase. It is also possible to use an electrode to which microorganisms acting as a reaction catalyst are attached.
  • the separator 24 prevents a short circuit between the electrodes (the anode 21 and the cathode 22), and is formed of a material that has flexibility and transmits protons (proton conductor). Specifically, a nonwoven fabric, a cellophane, a perfluorosulfonic acid type ion exchange membrane etc. can be used, for example.
  • Gas-liquid separation membrane 26 The gas-liquid separation membrane 26 does not permeate liquid but permeates only gas.
  • a PTFE PolyTetraFluoroethylene: polytetrafluoroethylene
  • the thickness and physical properties are not particularly limited as long as the fuel solution can be prevented from leaking and oxygen necessary for the reaction can be supplied to the cathode 5.
  • the material of the current collectors 3 and 6 is not particularly limited as long as it is a material that can be electrically connected to the outside and does not cause an electrochemical reaction in the biofuel cell.
  • the fuel tank 27 stores the fuel solution 4, and includes, for example, polyethylene, polystyrene, polypropylene, AS resin (Acrylonitylylylene Polymer), ABS resin (Acrylonitrile Butadiene Styrene Polymer), vinyl chloride resin, methacrylic resin, polyethylene terephthalate And various plastic materials, elastic bodies such as natural rubber and synthetic rubber, insulating metal oxides such as alumina, silica and ceramics.
  • the structure is not particularly limited, but at least the fuel solution 4 needs to be in contact with the anode 21 and the proton can move to the cathode 22.
  • a frame-like structure having a fuel injection port (not shown) and opened on the anode 21 and cathode 22 side can be used.
  • the distance between the anode 21 and the cathode 22 is preferably as short as possible.
  • a structure in which an anode, a cathode, and a separator are integrated is proposed by dissolving and applying a water repellent agent in an organic solvent and press-bonding with a hot press.
  • an enzyme deteriorates due to an organic solvent or heating, so that such a structure cannot be adopted at present.
  • one or more pressing members 28 are arranged in the fuel tank 27 to press the anode 21 and the cathode 22 from the inside of the cell.
  • the distance between the anode 21 and the cathode 22 can be shortened as a whole, and the proton moving speed can be increased.
  • the adhesion between the anode 21 and the cathode and the electric bodies 23 and 25 is improved, the resistance during current collection can be reduced. As a result, the power generation efficiency is increased and the output per unit volume can be increased.
  • the pressing member 28 includes, for example, various plastic materials such as polyethylene, polystyrene, polypropylene, AS resin, ABS resin, vinyl chloride resin, methacrylic resin, polyethylene terephthalate and polycarbonate, elastic bodies such as natural rubber and synthetic rubber, alumina, silica and It can be formed of an insulating metal oxide such as ceramics.
  • the shape of the pressing member 28 is not particularly limited, but may be a spherical shape, a prismatic shape, an anti-rectangular prism shape, or the like in addition to the cylindrical shape as shown in FIG. However, it is desirable to avoid a downward concave shape so that air does not accumulate in the fuel tank 27.
  • the thickness (height) of the pressing member 28 is larger than the thickness of the fuel tank 27, the adhesion between the fuel tank 27 and the separator 24 may be reduced, and liquid leakage may occur. Therefore, it is desirable that the thickness (height) of the pressing member 28 is the same as the thickness of the fuel tank 27 or slightly smaller than the thickness of the fuel tank 27 from the viewpoint of preventing liquid leakage. Furthermore, when a plurality of pressing members 28 are arranged, it is desirable to arrange them at regular intervals.
  • 4A and 4B are plan views showing examples of arrangement of the pressing member 28, and FIG. 4C is a plan view showing a conventional battery structure without the pressing member.
  • FIG. 5 is a graph showing the results of constant potential measurement for the biofuel cells of FIGS.
  • FIG. 6 is an exploded perspective view schematically showing another configuration of the power generation unit 11 of the biofuel cell 1 shown in FIG.
  • the same components as those of the biofuel cell 1 shown in FIG. 3 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • 3 and 4 show an example in which the cylindrical pressing member 28 is arranged, but the present disclosure is not limited to this, and extends in the width direction and the height direction as shown in FIG.
  • a press bar 48 in which a plurality of bars are integrated can also be used.
  • FIG. 7 shows time on the horizontal axis and the current value on the vertical axis, and a constant potential measurement was performed on a biofuel cell having a single cell structure configured as shown in FIG. 6 and a biofuel cell without a press bar.
  • the partition plate 12 includes, for example, various plastic materials such as polyethylene, polystyrene, polypropylene, AS resin, ABS resin, vinyl chloride resin, methacrylic resin, polyethylene terephthalate and polycarbonate, elastic bodies such as natural rubber and synthetic rubber, alumina, silica and ceramics. It can form with insulating metal oxides, such as.
  • the exterior plate 13 is provided with an air inlet for taking outside air into the battery.
  • the exterior plate 13 is made of various plastic materials such as polyethylene, polystyrene, polypropylene, AS resin, ABS resin, vinyl chloride resin, methacrylic resin, polyethylene terephthalate and polycarbonate, elastic bodies such as natural rubber and synthetic rubber, alumina, silica and It can be formed of an insulating metal oxide such as ceramics.
  • the height of the partition plate 12 is lower than the height of the exterior plate 13, and the other members have the same height as the partition plate 12. ing.
  • a recess that communicates with the fuel tank 27 of each power generation unit 11 is formed between the pair of exterior plates 13, and fuel is generated in all the power generation units 11 in which these are stacked. It becomes the fuel supply part 14 which can supply a solution.
  • the lid 3 has a shape that fits into the fuel inlet of each of the fuel supply unit 14 and each fuel tank 27.
  • polyethylene, polystyrene, polypropylene, AS resin, ABS resin, vinyl chloride resin, methacrylic resin, polyethylene terephthalate, and polycarbonate It can be formed of various plastic materials such as, elastic bodies such as natural rubber and synthetic rubber, and insulating metal oxides such as alumina, silica and ceramics. And after filling each electric power generation part 11 with the fuel solution 4, the fuel solution with which each electric power generation part 11 was filled by fitting the cover body 3 to the fuel inlet of the fuel supply part 14 and each fuel tank 27. 4 can be kept out of contact with each other.
  • FIG. 8 is a perspective view schematically showing a method of supplying the fuel solution 4 to the biofuel cell 1 of the present embodiment. As shown in FIG. 8, in the biofuel cell 1 of the present embodiment, the lid 3 is opened, and the fuel solution 4 is poured into a concave fuel supply unit 14 provided on the upper surface of the fuel cell body 2, for example.
  • the “fuel solution 4” supplied to the biofuel cell 1 of the present embodiment is a fuel component such as sugar, alcohol, aldehyde, lipid and protein, or a solution containing at least one of these fuel components.
  • the fuel component used in the biofuel cell 1 of the present embodiment include sugars such as glucose, fructose, and sorbose, alcohols such as methanol, ethanol, propanol, glycerin, and polyvinyl alcohol, formaldehyde, and acetaldehyde.
  • Examples include aldehydes, organic acids such as acetic acid, formic acid, and pyruvic acid.
  • fats and proteins, organic acids that are intermediate products of these sugar metabolisms, and the like can be used as fuel components.
  • the fuel supply unit 14 since the fuel supply unit 14 communicates with the fuel injection ports of all the power generation units 11 stacked, all the fuel solution 4 is injected into the fuel supply unit 14, The fuel solution 27 can be filled in the fuel tank 27. Then, after injecting the fuel solution 4, the lid 3 is fitted into the fuel supply part 14 and the fuel inlet of each fuel tank 27. In this biofuel cell 1, even when the injection amount of the fuel solution 4 is large, the excess fuel solution 4 is discharged out of the cell by fitting the lid 3. The independence of the solution 4 can be maintained.
  • the injection amount of the fuel solution 4 may be set to a position lower than the height of the partition plate 12.
  • the fuel supply unit 14 that communicates with the fuel inlet of each power generation unit 11 is provided, and the fuel solution is supplied to all the fuel tanks 27 in one operation. 4 can be filled.
  • all the fuel injection ports can be closed by the lid 3, the independence of the fuel solution 4 can be maintained even if the fuel supply unit 3 is common, and a short circuit of the power generation unit 11 can be prevented. Can do. ⁇ 2. First Modification of First Embodiment> [overall structure] FIG.
  • FIG. 9 is a cross-sectional view schematically illustrating a configuration of a biofuel cell according to a first modified example of the first embodiment of the present disclosure.
  • the same components as those of the biofuel cell 1 shown in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the lid 33 is provided with a filling amount adjustment unit 33 a for adjusting the filling amount of the fuel solution 4 in each power generation unit 3.
  • the structure of the filling amount adjustment part 33a is not specifically limited, For example, it can be set as a through-hole.
  • the lid 33 is provided with the filling amount adjusting unit 33a. Therefore, even when the fuel solution is injected to a position higher than the height of the partition plate 12, the filling in the lid 33 is performed. Liquid storage can be prevented by storing fuel in the amount adjusting unit 33a.
  • the configuration and effects other than those described above in the present modification are the same as those in the first embodiment described above. ⁇ 3. Second Modification of First Embodiment> [overall structure] FIG.
  • FIG. 10 is a cross-sectional view schematically illustrating a configuration of a biofuel cell according to a second modified example of the first embodiment of the present disclosure.
  • the same components as those of the biofuel cell 1 shown in FIG. 4 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • a filling amount adjusting unit 43 a for adjusting the filling amount of the fuel solution 4 in each power generation unit 3 is provided on the exterior plate 43 of the fuel cell main body 42. ing.
  • the configuration of the filling amount adjusting unit 43a is not particularly limited.
  • a configuration in which a through-hole is provided at the same position as the upper portion of the exterior plate 43 and the height of the partition plate 12 of the fuel supply unit 14 is provided. can do. Thereby, even when the fuel solution 4 is excessively injected from the fuel supply unit 14, it is discharged from the filling amount adjusting unit 43a.
  • the filling plate 43 is provided with the filling amount adjusting portion 43a, the fuel solution 4 can be suppressed to a position lower than the height of the partition plate 12, and the lid 3 is fitted. Sometimes, the fuel solution 4 can be prevented from overflowing.
  • the configuration and effects other than those described above in the present modification are the same as those in the first embodiment described above. ⁇ 4.
  • FIG. 11 is an exploded perspective view schematically showing the configuration of the power generation unit of the biofuel cell of the present embodiment.
  • the power generation unit 60 is provided with an anode 61 and a cathode 62, and for example, a fuel tank 68 and a separator 63 are arranged between them in this order.
  • current collectors 64 and 65 are disposed in contact with the anode 61 and the cathode 62, respectively.
  • the positions of the anode current collector 64 and the anode 61 and / or the positions of the cathode current collector 65 and the cathode 62 may be reversed.
  • oxidoreductase is present on the electrode surface of the anode 61 or the cathode 62 or both.
  • the surface of the electrode includes the entire outer surface of the electrode and the inner surface of the void inside the electrode, and the same applies to the following description.
  • pH test paper 66 is disposed in the fuel solution.
  • the anode 61 is a fuel electrode, and for example, an anode in which an oxidoreductase is immobilized on the surface of an electrode made of a conductive porous material can be used.
  • a conductive porous material known materials can be used, and in particular, carbon-based materials such as porous carbon, carbon pellets, carbon felt, carbon paper, carbon fiber, or a laminate of carbon fine particles. Material is preferred.
  • the enzyme immobilized on the surface of the anode 61 for example, when the fuel component is glucose, glucose dehydrogenase (GDH) that decomposes glucose can be used.
  • GDH glucose dehydrogenase
  • a coenzyme oxidase and an electron mediator are immobilized on the anode surface together with an oxidase that promotes and decomposes monosaccharide such as GDH. It is desirable.
  • a coenzyme oxidase is a coenzyme that is reduced by an oxidase (eg, NAD + , NADP + Etc.) and a reduced form of a coenzyme (for example, NADH, NADPH, etc.), such as diaphorase.
  • the electron mediator By the action of the coenzyme oxidase, electrons are generated when the coenzyme returns to the oxidized form, and the electrons are transferred from the coenzyme oxidase to the electrode via the electron mediator.
  • the electron mediator a compound having a quinone skeleton is preferably used, and a compound having a naphthoquinone skeleton is particularly preferable.
  • 2-amino-1,4-naphthoquinone ANQ
  • 2-amino-3-methyl-1,4-naphthoquinone ANQ
  • 2-methyl-1,4-naphthoquinone VK3
  • 2- Amino-3-carboxy-1,4-naphthoquinone ACNQ
  • the compound having a quinone skeleton for example, a compound having an anthraquinone skeleton such as anthraquinone-1-sulfonic acid, anthraquinone-2-sulfonic acid and anthraquinone-2-carboxylic acid, and derivatives thereof Can also be used. Furthermore, you may fix
  • polysaccharide refers to a polysaccharide in a broad sense and refers to all carbohydrates that produce two or more monosaccharides by hydrolysis, and includes oligosaccharides such as disaccharides, trisaccharides, and tetrasaccharides.
  • starch amylose, amylopectin, glycogen, cellulose, maltose, sucrose, and lactose. These are a combination of two or more monosaccharides, and any polysaccharide contains glucose as a monosaccharide of the binding unit.
  • Amylose and amylopectin are components contained in starch, and starch is a mixture of amylose and amylopectin.
  • glucoamylase is used as a polysaccharide degrading enzyme and glucose dehydrogenase is used as an oxidase degrading monosaccharide
  • a polysaccharide that can be decomposed into glucose by glucoamylase is used as the fuel component. can do.
  • polysaccharides examples include starch, amylose, amylopectin, glycogen and maltose.
  • glucoamylase is a degrading enzyme that hydrolyzes ⁇ -glucan such as starch to produce glucose
  • glucose dehydrogenase is an oxidase that oxidizes ⁇ -D-glucose to D-glucono- ⁇ -lactone.
  • the anode 61 is not limited to the one having the oxidoreductase immobilized on the surface. For example, if the oxidoreductase is present on the electrode surface, the anode 61 has an oxidoreductase, for example.
  • the cathode 62 is an air electrode and is in contact with the gas phase (air) directly or via the gas-liquid separation membrane 67.
  • the electrode constituting the cathode 62 is not particularly limited.
  • an electrode in which an oxidoreductase and an electron mediator are immobilized on the surface of an electrode made of a conductive porous material can be used.
  • a conductive porous material forming the cathode 62 a known material can be used, and in particular, a carbon-based material such as porous carbon, carbon pellet, carbon felt, carbon paper, carbon fiber, or a laminate of carbon fine particles.
  • Examples of the oxygen reductase immobilized on the cathode 62 include bilirubin oxidase, laccase, and ascorbate oxidase.
  • Examples of the electron mediator immobilized together with these enzymes include potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), potassium ferricyanide and potassium octacyanotungstate.
  • the cathode 62 is not limited to the one having the oxidoreductase immobilized on the surface. For example, if the oxidoreductase is present on the electrode surface, the cathode 62 has an oxidoreductase, for example.
  • the separator 63 prevents each electrode (the anode 61 and the cathode 62) from being short-circuited, and is formed of a material that has flexibility and transmits protons (proton conductor). Specifically, a nonwoven fabric, a cellophane, a perfluorosulfonic acid type ion exchange membrane etc. can be used, for example.
  • Current collector 64, 65 The material of the current collectors 64 and 65 is not particularly limited as long as it is a material that can be electrically connected to the outside and does not cause an electrochemical reaction in the biofuel cell.
  • the pH test paper 66 detects a change in the pH of the fuel solution as the fuel is consumed, and can be appropriately selected according to the type of fuel, the composition of the fuel solution, the degree of change in the pH, and the like. Further, the position where the pH test paper 66 is disposed is not particularly limited as long as it is in a position where it can contact the fuel solution and the color change can be confirmed from the outside through the transparent or translucent portion of the container. Good. For example, as power generation proceeds, the pH of the fuel solution near the anode 61 tends to be acidic, and the pH of the fuel solution near the cathode 62 tends to the basic side.
  • the pH test paper 66 is arranged in the vicinity of the anode 61, a paper whose color changes in a range lower than the fuel solution is selected, and when the pH test paper 66 is arranged in the vicinity of the cathode 62. What is necessary is just to select what changes color in the range whose pH is higher than a fuel solution. From the viewpoint of ease of observation, the pH test paper 66 is desirably disposed in the vicinity of the anode 61 as shown in FIG.
  • a gas-liquid separation membrane 67 can be disposed between the cathode 62 and the gas phase (air) as necessary.
  • the gas-liquid separation block 67 does not allow liquid to permeate, and allows only gas to permeate.
  • a PTFE PolyTetraFluoroethylene: polytetrafluoroethylene
  • the thickness and physical properties are not particularly limited as long as the fuel solution can be prevented from leaking and oxygen necessary for the reaction can be supplied to the cathode 62.
  • the container (not shown) is partially or entirely made of a transparent or translucent material so that the pH test paper 66 can be seen.
  • the material is not particularly limited, but the transparent or translucent portion can be formed of, for example, a polyolefin resin such as polyethylene or polypropylene, an acrylic resin, or a fluorine resin. Thereby, the pH change of a fuel solution can be confirmed easily visually.
  • the “fuel solution” supplied to the biofuel cell of the present embodiment is a fuel component such as sugar, alcohol, aldehyde, lipid and protein, or a solution containing at least one of these fuel components.
  • Examples of the fuel component used in the biofuel cell of the present embodiment include sugars such as glucose, fructose, and sorbose, alcohols such as methanol, ethanol, propanol, glycerin, and polyvinyl alcohol, and aldehydes such as formaldehyde and acetaldehyde. And organic acids such as acetic acid, formic acid and pyruvic acid. In addition, fats and proteins, organic acids that are intermediate products of these sugar metabolisms, and the like can be used as fuel components. As described above in detail, in the biofuel cell according to the present embodiment, the pH test paper 66 is disposed in the fuel solution. Therefore, the consumption of the fuel component is reduced by changing the pH without using electric power for detection. Can be confirmed.
  • the storage container is transparent or translucent so that the pH test paper 66 can be seen, it is possible to visually recognize deterioration in battery performance due to fuel consumption. As a result, it is possible to easily determine the replacement timing of the fuel solution without analyzing the fuel solution.
  • the pH test paper 66 which is a pH detection unit
  • the battery is not complicated or enlarged. . ⁇ 5.
  • the present disclosure is not limited to this, and the pH detection unit may What is necessary is just to recognize the change of pH by the change. Therefore, in the biofuel cell of the present embodiment, a pH indicator is used instead of the pH test paper, and the consumption of the fuel component is confirmed from the color change of the fuel solution itself.
  • a pH indicator is used instead of the pH test paper, and the consumption of the fuel component is confirmed from the color change of the fuel solution itself.
  • the type of pH indicator is not particularly limited, and can be appropriately selected according to the type of fuel, the composition of the fuel solution, the degree of change in pH, and the like.
  • the addition amount of the pH indicator described above is not particularly limited as long as the change in the color of the fuel solution can be visually confirmed through the container. Further, the addition timing is not particularly limited, and may be added in advance to the fuel solution filled in the fuel cell, for example, or may be added to the fuel solution during power generation. [Container] In the biofuel cell of this embodiment, a part or all of the container is formed of a transparent or translucent material so that a change in the color of the fuel solution can be confirmed.
  • the color change of at least the fuel solution near the anode 61 or the cathode 62 can be visually confirmed.
  • the pH indicator is added to the fuel solution, the consumption of the fuel component can be confirmed by the color change without using electric power for detection. it can.
  • at least a part of the container is transparent or translucent so that the fuel solution can be seen, it is possible to visually recognize deterioration of the cell performance due to fuel consumption.
  • FIG. 12 is an exploded perspective view schematically showing the configuration of the biofuel cell of the present modification
  • FIGS. 13 and 14 are diagrams showing a configuration example of the storage container.
  • the biofuel cell of this modification performs fuel supply and fuel agitation using centrifugal force.
  • a power generation unit is provided in a circular container as shown in FIGS. 13 and 14 in a plan view.
  • the disk-shaped member which comprises is laminated
  • the power generation unit is provided with an anode 61 and a cathode 62, and a separator 63 is disposed between them. Further, current collectors 64 and 65 are disposed in contact with the anode 61 and the cathode 62, respectively.
  • a pH test paper (not shown) is disposed in the fuel solution, or a pH indicator is added to the fuel solution.
  • FIG. 12 shows an example in which the anode 61, the anode current collector 64, the separator 63, the cathode 62, the cathode current collector 65, and the gas-liquid separation membrane 67 are arranged in this order.
  • the position of the anode 61 and / or the positions of the cathode current collector 65 and the cathode 62 may be reversed.
  • a lower lid 58 and a side wall 59 as shown in FIG. 13 are integrated, and an upper lid 51 is fitted therein, or an upper lid 51 and a lower lid 58 as shown in FIG.
  • a structure having a side wall 59 sandwiched therebetween can be used.
  • a fuel injection port 51a is provided at the center of the upper lid 51 of the housing container, and an air introduction port 58a for taking outside air into the battery is provided in the lower lid 58.
  • the container (the upper cover 51, the lower cover 58) is partially or entirely formed of a transparent or translucent material. Thereby, the color change of the pH test paper immersed in the fuel solution in the power generation unit or the pH indicator dissolved in the fuel solution can be visually confirmed from the transparent or translucent portion.
  • a discharge port that can be opened and closed by a lid or the like is provided on the side surface of the storage container (the upper lid 51 or the lower lid 58), and the fuel solution (waste liquid) in the power generation unit is discharged as necessary. It may be possible.
  • a groove 51b can be provided on the surface of the upper lid 51 on the anode 2 side.
  • the shape of the groove 51b is not particularly limited, and examples thereof include a radial shape, a concentric circular shape, and a helical shape.
  • the fuel is directed from the fuel inlet 51a toward the center of the anode 61 at the start of power generation and when a decrease in fuel component concentration is confirmed due to a change in pH test paper or pH indicator color.
  • a solution is introduced.
  • the cell main body is rotated around the fuel injection port 51a, so that the injected fuel solution spreads radially and the fuel component can be spread over the entire anode 61. it can.
  • the diffusion in the electrode becomes gentle. In this way, the fuel solution can be quickly diffused by centrifugal force by rotating the battery around the center. Is possible.
  • the method of rotating the biofuel cell is not particularly limited, and for example, there is a method of rotating the biofuel cell by applying a force to the rotating shaft (fuel injection port 51a) or the side surface of the container. At that time, the operator may apply the force directly, but the force can also be applied indirectly by combining pulleys, gear boards, strings or pulleys. Further, the concave and convex portions may be formed on the side surface of the storage container and may be rotated in combination with a gear board. This method is effective when a plurality of biofuel cells are connected in parallel.
  • the biofuel cell may be rolled sideways.
  • a waste liquid discharge port that can be opened and closed by a lid is provided at a position perpendicular to the rotation axis such as the side surface of the container, and the spent fuel solution is utilized by utilizing centrifugal force. (Waste liquid) may be discharged.
  • the lid is closed during power generation, the lid is opened after power generation to release the waste liquid discharge port, and the biofuel cell is rotated.
  • the used fuel solution can be easily and reliably removed from the power generation unit.
  • the biofuel cell of this modification When removing the waste liquid, for example, by rotating the biofuel cell in a container such as a waste liquid receiver, it is possible to prevent contamination to the surroundings and scattering of the waste liquid.
  • the power generation performance can be recovered by rotating the cell. Thereby, the concentration distribution of the fuel solution in the power generation unit can be eliminated, and the power generation performance can be effectively recovered.
  • output recovery can be achieved more efficiently by rotating the biofuel cell according to the pH change in the power generation unit.
  • the battery itself since the battery itself is rotatable, even when a high concentration fuel solution is used, the fuel component can be diffused immediately after fuel injection. Thereby, the reaction efficiency of fuel improves.
  • the fuel utilization efficiency is also improved. Furthermore, by providing a waste liquid discharge port on the side wall 59 of the storage container, the spent fuel solution (waste liquid) can be quickly removed from the power generation unit using centrifugal force.
  • the biofuel cell can be combined with an existing top-of-the-line toy to decorate the top by illuminating the light emitting element, or to change the rotation speed of the top by rotating the motor. Note that the biofuel cell of this modification has a mortar shape (tapered shape) in which the power generation portion is inclined from the center toward the outside, that is, the center portion into which the fuel solution is injected is low and becomes higher as it goes outward. It is good also as a structure.
  • the pressing member has a structure in which a plurality of rod-shaped members extending in the width direction and the height direction are integrated.
  • this indication can also take the following structures.
  • a detection unit for detecting a pH change of the fuel solution by a color change A storage container in which the power generation unit is stored;
  • a pH indicator is added to the fuel solution as the detection unit.

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

Abstract

L'invention concerne une batterie au biocarburant ayant une structure d'éléments empilés qui comprend des parties de génération d'énergie connectées en série, chacune équipée d'une ou de deux électrodes (anode et/ou cathode) ayant une oxydoréductase présente sur la surface de celles-ci, une partie d'alimentation de carburant qui communique avec les entrées de carburant des parties de génération d'énergie étant formée. Une solution de carburant est introduite à travers la partie d'alimentation de carburant, puis la partie d'alimentation de carburant et les entrées de carburant sont fermées avec un couvercle pour empêcher la solution de carburant introduite dans chaque partie de génération d'énergie de venir en contact avec la solution de carburant introduite dans un autre. La batterie au biocarburant, qui comprend des parties de génération d'énergie qui sont chacune équipées d'une ou de deux électrodes ayant une oxydoréductase présente sur la surface de celles-ci et qui ont chacune été disposées dans un boîtier, comporte une partie de détection de pH destinée à détecter un changement dans le pH de la solution de carburant au moyen d'un changement de couleur. Par ailleurs, au moins la partie du boîtier à travers laquelle la partie de détection peut être observée est rendue transparente ou translucide. La partie de détection de pH peut être configurée, par exemple, par mise en place d'un papier d'essai de pH dans la solution de carburant ou par l'ajout d'un indicateur de pH à la solution de carburant.
PCT/JP2012/067250 2011-07-06 2012-06-29 Batterie au biocarburant WO2013005814A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-149854 2011-07-06
JP2011149854A JP2013016413A (ja) 2011-07-06 2011-07-06 バイオ燃料電池
JP2011-169024 2011-08-02
JP2011169024A JP2013033630A (ja) 2011-08-02 2011-08-02 バイオ燃料電池

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WO2010037138A2 (fr) * 2008-09-29 2010-04-01 Akermin, Inc. Pile à combustible direct anionique à alcool dotée d’une biocathode
JP2010516017A (ja) * 2007-01-05 2010-05-13 アケルミン・インコーポレイテッド バイオアノード及びバイオカソードのスタックアセンブリ
JP2010219021A (ja) * 2009-02-20 2010-09-30 Sony Corp 燃料電池、電子機器及びバイオセンサー
WO2011046006A1 (fr) * 2009-10-16 2011-04-21 オリンパス株式会社 Pile à combustible, batterie, et électrode pour pile à combustible

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JP2006234788A (ja) * 2004-07-23 2006-09-07 Canon Inc 酵素電極、酵素電極を有するデバイス、センサ、燃料電池、電気化学的反応装置
JP2010516017A (ja) * 2007-01-05 2010-05-13 アケルミン・インコーポレイテッド バイオアノード及びバイオカソードのスタックアセンブリ
JP2009048848A (ja) * 2007-08-20 2009-03-05 Sony Corp 燃料電池
JP2009094008A (ja) * 2007-10-11 2009-04-30 Olympus Corp 乾電池型燃料電池、乾電池型燃料電池の製造方法
JP2009140646A (ja) * 2007-12-04 2009-06-25 Sony Corp 新規な電力供給装置及び電子機器
WO2010037138A2 (fr) * 2008-09-29 2010-04-01 Akermin, Inc. Pile à combustible direct anionique à alcool dotée d’une biocathode
JP2010219021A (ja) * 2009-02-20 2010-09-30 Sony Corp 燃料電池、電子機器及びバイオセンサー
WO2011046006A1 (fr) * 2009-10-16 2011-04-21 オリンパス株式会社 Pile à combustible, batterie, et électrode pour pile à combustible

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WO2016194374A1 (fr) * 2015-06-05 2016-12-08 パナソニック株式会社 Complexe à électrode, et pile à combustible microbienne et dispositif de traitement des eaux l'utilisant
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