WO2013168536A1 - 直接アルミニウム燃料電池及び電子機器 - Google Patents
直接アルミニウム燃料電池及び電子機器 Download PDFInfo
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- WO2013168536A1 WO2013168536A1 PCT/JP2013/061586 JP2013061586W WO2013168536A1 WO 2013168536 A1 WO2013168536 A1 WO 2013168536A1 JP 2013061586 W JP2013061586 W JP 2013061586W WO 2013168536 A1 WO2013168536 A1 WO 2013168536A1
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- positive electrode
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- direct aluminum
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M1/00—Apparatus for enzymology or microbiology
- C12M1/40—Apparatus specially designed for the use of free, immobilised, or carrier-bound enzymes, e.g. apparatus containing a fluidised bed of immobilised enzymes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
- H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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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
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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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
- H01M2300/00—Electrolytes
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
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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
Definitions
- This disclosure relates directly to aluminum fuel cells and electronic equipment. More specifically, the present disclosure includes a direct aluminum fuel cell that generates electricity using a negative electrode having a material containing aluminum as a fuel and oxygen in the air as a positive electrode active material, and the direct aluminum fuel cell. It relates to various electronic devices.
- an air battery also referred to as a metal-air battery
- a metal-air battery uses a metal having a high energy density as a negative electrode active material and uses oxygen in the air as a positive electrode active material, it can operate as a half-cell, and the amount of electrode active material is Half is enough. Therefore, the air battery can theoretically obtain a large energy density.
- an aluminum air battery using aluminum as a negative electrode is known and is expected as a battery having a large capacity (see, for example, Patent Documents 1 to 3).
- the alkaline electrolytic solution strongly corrodes aluminum, or the alkaline electrolytic solution gradually becomes neutral by absorbing carbon dioxide in the air. This causes a problem that the positive electrode is deteriorated.
- an object of the present disclosure is to provide a direct aluminum fuel cell capable of preventing corrosion of aluminum constituting a negative electrode used as fuel and preventing deterioration of the positive electrode, and an electronic device including the direct aluminum fuel cell. It is to provide.
- a direct aluminum fuel cell according to the first aspect of the present disclosure is provided.
- a negative electrode having a material comprising aluminum, and A positive electrode that reduces oxygen under near neutral conditions;
- An electrolyte having a pH of 3 or more and 10 or less is used,
- the electrolytic solution contains a buffer substance.
- a direct aluminum fuel cell according to the second aspect of the present disclosure for achieving the above object is as follows: A negative electrode having a material comprising aluminum, and A positive electrode that reduces oxygen under near neutral conditions; Have
- an electronic device of the present disclosure for achieving the above object includes at least one direct aluminum fuel cell according to the first aspect or the second aspect of the present disclosure.
- the direct aluminum fuel cell according to the first aspect or the second aspect of the present disclosure the direct aluminum fuel cell according to the first aspect or the second aspect of the present disclosure provided in the electronic device of the present disclosure (hereinafter referred to as these directly collectively aluminum fuel cell, in the "direct disclosure aluminum fuel cells” may be referred to as), pK a of the buffer substance is 4 or more, preferably 10 or less, thereby, the electrolyte PH can be maintained at 3 or more and 10 or less. Buffer substances, pK a is 4 or more, as long as 10 or less, may be used What basically, is selected as necessary.
- the buffer substance is preferably contained in the electrolytic solution in an amount of 0.2 mol or more per liter of the electrolytic solution.
- the upper limit value of the solubility of the buffer substance in the electrolytic solution can be mentioned, and the amount of the buffer substance contained in the electrolytic solution is the solubility of the buffer substance in the electrolytic solution. It is more preferable that it is close to the upper limit value.
- the electrolytic solution can be in a form containing halide ions, and in this case, the halide ions are preferably chloride ions.
- the positive electrode can be configured to reduce oxygen under conditions where the pH is 3 or more and 10 or less.
- the positive electrode may be an enzyme-immobilized electrode on which oxygen reductase is immobilized, or a material that reduces oxygen, such as carbon (including charcoal), metal, carbon and metal, or catalyst (specifically Specifically, an electrode including an oxygen reduction catalyst which is a catalyst for reducing oxygen may be used. Alternatively, the positive electrode may be an electrode including a catalyst that can reduce oxygen by four electrons under conditions near neutrality (for example, the catalyst is an enzyme). Typically, direct aluminum fuel cells have a separator between the negative electrode and the positive electrode.
- the shape of the negative electrode is selected as necessary, and is, for example, a foil shape, a sheet shape, or a plate shape.
- the negative electrode In order to increase the contact area of the negative electrode with oxygen, if necessary, at least a part of the negative electrode, preferably almost all or all of the negative electrode, is formed in a mesh shape or made of a porous material.
- the negative electrode is made of an aluminum foil.
- the negative electrode is configured to be replaceable as necessary.
- the direct aluminum fuel cell is configured so that insoluble matter as a by-product can be removed at the same time when the negative electrode is replaced.
- Electronic devices may be basically any type, including both portable and stationary types, but specific examples include mobile phones, mobile devices, robots, personal computers. , Game devices, camera-integrated VTRs (video tape recorders), in-vehicle devices, various household electric products, industrial products, and the like.
- VTRs video tape recorders
- the positive electrode oxygen is reduced under neutral conditions, so that self-corrosion of aluminum can be prevented, and the positive electrode is deteriorated as in the case of using an alkaline solution as the electrolytic solution. there is no problem.
- a novel direct aluminum fuel cell capable of preventing corrosion of aluminum constituting the negative electrode used as the fuel and further preventing deterioration of the positive electrode. By using this excellent direct aluminum fuel cell, a high-performance electronic device or the like can be realized.
- FIG. 1A and 1B are schematic cross-sectional views of a direct aluminum fuel cell of Example 1 and its modification, respectively.
- FIG. 2 is a graph showing the relationship between the corrosion amount of aluminum and pH.
- FIG. 3 is a graph showing the output characteristics of the direct aluminum fuel cell of Example 1.
- FIG. 4 is a graph showing the amount of charge taken from the direct aluminum fuel cell of Example 1.
- FIG. 5 is a graph showing the results of an experiment conducted for examining the influence of chloride ions on the oxidation reaction of an aluminum foil having an area of 1 cm 2 .
- 6 is a schematic cross-sectional view of the direct aluminum fuel cell of Example 3.
- FIG. FIG. 7 is a graph showing the output characteristics of the direct aluminum fuel cell of Example 3. 8A, FIG. 8B, FIG. 8C and FIG.
- FIG. 8D are schematic cross-sectional views of the direct aluminum fuel cell of Example 4, and schematic views of the state before and after use of the fuel cartridge of the direct aluminum fuel cell of Example 4, respectively. It is sectional drawing and the typical sectional view of the state after the fuel use of the direct aluminum fuel cell of Example 4.
- FIG. 9 is a schematic cross-sectional view for explaining a method for replacing the fuel cartridge of the direct aluminum fuel cell according to the fourth embodiment.
- Example 1 directly aluminum fuel cell, its manufacturing method and its operation
- Example 2 Modification of Example 1
- Example 3 another modification of Example 1 4
- Example 4 modification of Examples 1 to 3
- FIG. 1A A schematic cross-sectional view of the direct aluminum fuel cell of Example 1 is shown in FIG. 1A.
- the direct aluminum fuel cell of Example 1 is A negative electrode 11 having a material containing aluminum, and A positive electrode 12 for reducing oxygen under neutral conditions; Furthermore, a separator 13 is disposed between the negative electrode 11 and the positive electrode 12.
- a current collector 14 is electrically connected to the upper surface of the negative electrode 11, and a current collector 15 is electrically connected to the lower surface of the positive electrode 12.
- the negative electrode 11, the positive electrode 12, and at least the portion of the separator 13 between the negative electrode 11 and the positive electrode 12 are immersed in the electrolytic solution.
- the separator 13 is filled with an electrolytic solution, and constitutes an electrolyte layer that conducts aluminum ions between the negative electrode 11 and the air electrode 12.
- the material containing aluminum constituting the negative electrode 11 is preferably a material containing aluminum as a main component, for example, aluminum alone or various aluminum alloys.
- the shape of the negative electrode 11 is not particularly limited, and may be any of a foil shape, a sheet shape, a plate shape, and the like, and the shape may be any of a bulk shape, a mesh shape, a porous shape, and the like.
- the positive electrode 12 reduces oxygen under neutral conditions, for example, pH of 3 or more and 10 or less, preferably 3 or more and 9 or less, more preferably 3 or more and 8 or less.
- an enzyme-immobilized electrode in which an oxygen reductase is immobilized is used as the positive electrode 12.
- oxygen reductase include, but are not limited to, bilirubin oxidase, laccase, and ascorbate oxidase.
- an electron mediator that transfers electrons to and from the positive electrode 12 is also immobilized on the positive electrode 12.
- the electron mediator include, but are not limited to, potassium hexacyanoferrate and potassium octacyanotungstate.
- the separator 13 In the positive electrode 12, in the presence of oxygen reductase, oxygen in the air is reduced by protons (H + ) from the separator 13 filled with the electrolyte and electrons from the negative electrode 11 to generate water.
- the material constituting the separator 13 include porous films such as polyethylene and polypropylene, and nonwoven fabrics.
- the material for the nonwoven fabric include various organic polymer compounds such as polyolefin, polyester, cellulose, and polyacrylamide, but are not limited thereto.
- the current collector 14 is typically composed of a metal mesh.
- the material of the metal mesh is not particularly limited as long as it can withstand the use environment of the aluminum fuel cell directly. Generally, titanium (Ti), nickel (Ni), stainless steel (for example, SUS304) or the like is used. Can be mentioned.
- the hole diameter of the metal mesh is not particularly limited, and is selected as necessary.
- the current collector 15 is configured to be permeable to the electrolytic solution.
- the current collector 15 is typically formed of a metal mesh, like the current collector 14.
- an electrolytic solution having a pH of 3 to 10 is preferably used, and the electrolytic solution contains a buffer substance.
- pK a of the buffer substance is 4 or more and 10 or less.
- the buffer substance include citric acid, ammonium chloride, phosphoric acid, trishydroxymethylaminomethane, a compound containing an imidazole ring, dihydrogen phosphate ion (H 2 PO 4 ⁇ ), 2-amino-2-hydroxymethyl-1 , 3-propanediol (abbreviated tris), 2- (N-morpholino) ethanesulfonic acid (MES), cacodylic acid, carbonic acid (H 2 CO 3 ), hydrogen citrate ion, N- (2-acetamido) iminodiacetic acid (ADA), piperazine-N, N′-bis (2-ethanesulfonic acid) (PIPES), N- (2-acetamido) -2-aminoethanesulfonic acid
- Examples of substances that generate dihydrogen phosphate ions include sodium dihydrogen phosphate (NaH 2 PO 4 ) and potassium dihydrogen phosphate (KH 2 PO 4 ).
- Examples of the compound containing an imidazole ring include imidazole, triazole, pyridine derivative, bipyridine derivative, imidazole derivative (histidine, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, imidazole-2-carboxylic acid Ethyl, imidazole-2-carboxaldehyde, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazol-1-yl-acetic acid, 2-acetylbenzimidazole, 1-acetylimidazole, N-acetylimidazole, 2 -Aminobenzimidazole, N- (3-aminopropyl) imid
- the electrolyte includes, for example, a group consisting of hydrochloric acid (HCl), acetic acid (CH 3 COOH), phosphoric acid (H 3 PO 4 ), and sulfuric acid (H 2 SO 4 ) in addition to the buffer substance. At least one selected acid may be added as a neutralizing agent.
- the electrolyte solution containing the buffer substance may contain, for example, a substance containing halide ions (chloride ions, bromide ions, iodide ions, fluoride ions, etc.).
- halide ions chloride ions, bromide ions, iodide ions, fluoride ions, etc.
- examples of the substance containing chloride ions include NaCl and KCl.
- a polytetrafluoroethylene (PTFE) membrane is preferably used as the gas-liquid separation membrane constituting the container for storing the electrolytic solution, but is not limited thereto.
- the shape of the container is selected as necessary.
- Examples of the shape of the battery case (container) that stores the positive electrode, the negative electrode, the separator, the electrolytic solution, and the like include a coin type, a flat plate type, a cylindrical type, and a laminate type.
- the battery case may be an open-air type having a structure in which at least the positive electrode can sufficiently come into contact with the atmosphere, or a sealed type provided with a gas (air) introduction pipe and an exhaust pipe.
- the current collector 14 is electrically connected to the upper surface of the negative electrode 11.
- the positive electrode 12 is immersed in an enzyme solution in which oxygen reductase is dissolved or the enzyme solution is applied to the positive electrode 12 to form the positive electrode 12 on which the oxygen reductase is immobilized
- the current collector 15 is electrically connected to.
- the separator 13 is sandwiched between the negative electrode 11 and the positive electrode 12, and the negative electrode 11, the positive electrode 12, and the separator 13 are impregnated with the electrolytic solution 17.
- the direct aluminum fuel cell shown in FIG. 1A can be obtained.
- FIG. 1B shows a schematic cross-sectional view of a modification of the direct aluminum fuel cell.
- the entire negative electrode 11, the entire positive electrode 12, and at least the portion of the separator 13 between the negative electrode 11 and the positive electrode 12 are immersed in an electrolytic solution 17 placed in a container 16 made of a gas-liquid separation membrane.
- Such a direct aluminum fuel cell is disposed in the container 16 so as to include the whole of the negative electrode 11, the whole of the positive electrode 12, and at least the part of the separator 13 between the negative electrode 11 and the positive electrode 12, and the container 16 is electrolyzed. It can be obtained by putting the liquid 17 and sealing the container 16.
- the structure in which the end portion of the separator 13 protrudes from the container 16 allows the space between the positive electrode 12 and the negative electrode 11 to be completely separated, and the reaction product (aluminum hydroxide) at the negative electrode 11 is transferred to the positive electrode. It can prevent moving to the side. If the reaction product does not move, the battery life can be extended.
- At least one of them may be formed integrally with the separator 13.
- the negative electrode 11 and the positive electrode 12 are formed integrally with the separator 13
- one of the negative electrode 11 and the positive electrode 12 is formed on one surface of the separator 13
- the other of the negative electrode 11 and the positive electrode 12 is formed on the other surface of the separator 13. What is necessary is just to form.
- Al 3+ moves from the negative electrode 11 through the separator 13 to the positive electrode 12 to generate electric energy.
- the positive electrode 12 in the presence of an enzyme that decomposes oxygen, oxygen in the air is reduced by H + from the separator 13 filled with the electrolytic solution 17 and electrons from the negative electrode 11, and water is generated.
- Example 1 4 or more in the electrolyte 17, contains buffering substances having 10 or less of pK a, by the action of the buffer substance, near neutral pH of the surface of the anode 11 (e.g., Since the pH can be maintained at 3 or more and 10 or less, aluminum does not self-corrode and promotes generation of hydrogen gas. That is, the relationship between the corrosion amount of aluminum and the pH is shown in FIG. 2. When the pH is in the range of 3 or more and 10 or less, the corrosion hardly occurs or the corrosion amount is extremely small, thereby suppressing the generation of hydrogen gas. be able to.
- An aluminum fuel cell was produced directly as follows. That is, a square aluminum foil having a size of 10 mm ⁇ 10 mm ⁇ 12 ⁇ m was used as the negative electrode 11, and a titanium mesh was electrically connected to the aluminum foil as the current collector 14.
- a positive electrode 12 an enzyme-immobilized electrode in which bilirubin oxidase (BOD) is immobilized as an oxygen reductase on a porous carbon electrode having a size of 10 mm ⁇ 10 mm ⁇ 2 mm is used, and a titanium mesh is used as a current collector 15 on the enzyme-immobilized electrode. Were electrically connected. And the separator 13 which consists of a nonwoven fabric was pinched
- BOD bilirubin oxidase
- the thus obtained laminate of negative electrode 11 / separator 13 / positive electrode 12 was placed in a container 16 made of a PTFE film, and electrolyte solution 17 was injected into container 16 and sealed.
- the electrolytic solution 17 is made of 3 mol / liter NaCl, contains imidazole as a buffer substance, HCl as a neutralizing agent, and has a pH of 7.
- the buffer substance is contained in an amount of 2 mol per liter of the electrolyte.
- FIG. 3 shows the results of measuring the output characteristics of the direct aluminum fuel cell thus produced at a cell voltage of 0.7V. Approximately 3500 seconds after the start of power generation (discharge start), all the aluminum foil was eluted and power generation was completed. The maximum current density was 0.013 A / cm 2 and the output was about 10 mW / cm 2 .
- FIG. 4 shows the amount of charge taken from the start of power generation to the end of power generation. It can be seen that it has a capacity of 1.9 Wh per gram of aluminum. After the end of power generation, by-product aluminum hydroxide (Al (OH) 3 ) remained in the electrolyte solution 17 as an insoluble material.
- Al (OH) 3 by-product aluminum hydroxide
- FIG. 5 shows the result of the oxidation reaction of the aluminum foil having an area of 1 cm 2 by changing the electrolytic solution.
- an electrolytic solution an aqueous solution containing 1 mol / liter NaCl, a saturated concentration of KCl, and 1 mol / liter of KNO 3 was used. From FIG. 5, the oxidation reaction hardly proceeds in the electrolyte containing KNO 3 . However, it can be seen that the oxidation reaction proceeds in the electrolyte containing NaCl or KCl. This means that inclusion of chloride ions, more generally halide ions, in the electrolyte plays an important role in the progress of the oxidation reaction.
- an enzyme-immobilized electrode that uses a material containing aluminum as the negative electrode 11 as fuel and decomposes oxygen under conditions near neutrality as the positive electrode 12 By using this, it is possible to prevent corrosion of aluminum constituting the negative electrode 11 used as the fuel and to prevent the deterioration of the positive electrode 12.
- This direct aluminum fuel cell is excellent in that the electrolyte solution 17 is near neutral and safe.
- Example 2 is a modification of Example 1.
- citric acid was used in place of imidazole as a buffer substance contained in the electrolytic solution 17.
- the buffer substance is contained in an amount of 1 mol per liter of the electrolyte.
- an aluminum fuel cell was produced directly in the same manner as in Example 1.
- a result equivalent to that of Example 1 was obtained, but after completion of power generation, aluminum hydroxide as a by-product remained in the electrolyte 17 as an insoluble matter. There wasn't.
- Example 3 is also a modification of Example 1.
- the positive electrode 12 is different from the direct aluminum fuel cell of Example 1.
- the positive electrode 12 is made of, for example, an electrode material that can reduce oxygen, or an electrode in which a catalyst that can reduce oxygen is supported on the electrode material.
- the electrode material include carbon and metal.
- examples of carbon include at least one selected from the group consisting of carbon particles, carbon sheets, and carbon fibers.
- the carbon particles include, for example, at least one selected from the group consisting of activated carbon, carbon black, and biocarbon, but may be other than these.
- the activated carbon include wood charcoal such as oak charcoal, kunugi charcoal, cedar charcoal, oak charcoal, hinoki charcoal, rubber charcoal, bamboo charcoal, oga charcoal, coconut shell charcoal, and the like.
- Examples of carbon black include furnace black, acetylene black, channel black, thermal black, ketjen black, and the like. Among these, ketjen black is preferable.
- Biocarbon is made from plant-derived materials with a silicon (silicon) content of 5% by weight or more.
- the specific surface area by nitrogen BET method is 10 m 2 / gram or more, and the silicon content is 1% by weight or less.
- a porous carbon material having a pore volume of 0.1 cm 3 / g or more by the BJH method and the MP method (see Patent Document 4).
- biocarbon is produced as follows, for example. That is, first, the ground rice husk (produced in Kagoshima Prefecture, Isehikari rice husk) was carbonized by heating in a nitrogen stream at 500 ° C. for 5 hours to obtain a carbide.
- the porous carbon material precursor is subjected to an acid treatment by immersing it overnight in a 46% by volume hydrofluoric acid aqueous solution to remove SiO 2 , or alternatively, the porous carbon material precursor is Alkali treatment was performed by immersing in an aqueous sodium hydroxide solution overnight to remove SiO 2 , followed by washing with water and ethyl alcohol until pH 7 was reached. And the porous carbon material, ie, biocarbon, is obtained by making it dry at the end.
- the positive electrode 12 When the positive electrode 12 is made of metal, examples of the metal include cobalt (Co), iridium (Ir), platinum (Pt), silver (Ag), gold (Au), ruthenium (Ru), and rhodium (Rh). , Osmium (Os), niobium (Nb), molybdenum (Mo), indium (In), zinc (Zn), manganese (Mn), iron (Fe), titanium (Ti), vanadium (V), chromium (Cr) At least one metal selected from the group consisting of palladium (Pd), rhenium (Re), tantalum (Ta), tungsten (W), zirconium (Zr), germanium (Ge) and hafnium (Hf), or Mention may be made of alloys.
- catalyst materials include manganese dioxide (MnO 2 ) (electrolytic manganese dioxide (EMD) and the like), tricobalt tetroxide (Co 3 O 4 ), nickel oxide (NiO), iron oxide (III) (Fe 2 O 3 ), ruthenium oxide (IV) (RuO 2 ), copper (II) oxide (CuO), vanadium pentoxide (V 2 O 5 ), molybdenum oxide (VI) (MoO 3 ), yttrium oxide (III) (Y Examples thereof include various inorganic ceramics such as 2 O 3 ) and iridium oxide (IV) (IrO 2 ).
- the catalyst material for example, various noble metals such as gold (Au), platinum (Pt), palladium (Pd), transition metal oxides, organometallic complexes, and polymers thereof (specifically, for example, Transition metal porphyrin, phthalocyanine, polymerized porphyrin polymerized by transition metal porphyrin, polymerized phthalocyanine polymerized by phthalocyanine), perovskite, and cobalt salt pyrolyzed with polyacrylonitrile and its Mention may be made of at least one material selected from the group consisting of pyrolysis products.
- catalyst materials such as LaBO 3 (B: Mn, Co) -based perovskite oxides, nitrides, sulfides; La 1-x A ′ x Co 1-y Fe y O 3 (provided that A As for ', Sr or Ca, x, and y are 0.2 to 0.5).
- the direct aluminum fuel cell of Example 3 can be the same as the direct aluminum fuel cell of Example 1 except that the configuration of the positive electrode 12 is different.
- FIG. 1 A schematic cross-sectional view of a direct aluminum fuel cell is shown in FIG.
- the whole of the negative electrode 11, the positive electrode 12, and the separator 13 is immersed in an electrolytic solution 17 placed in a container 16 made of a gas-liquid separation membrane.
- the direct aluminum fuel cell of Example 3 is the direct aluminum fuel cell of Example 1 except that the positive electrode 12 is formed from an electrode material that reduces oxygen or is formed by supporting a catalyst that reduces oxygen on the electrode material. It can be manufactured in the same manner as the aluminum fuel cell.
- the operation of the direct aluminum fuel cell of Example 3 is also the same as that of the direct aluminum fuel cell of Example 1.
- a direct aluminum fuel cell of Example 3 was produced as follows. That is, a square aluminum mesh having a size of 10 mm ⁇ 10 mm ⁇ 170 ⁇ m was used as the negative electrode 11, and a titanium mesh was electrically connected to the aluminum mesh as the current collector 14. Biocarbon was applied to a separator 13 made of a nonwoven fabric having a size of 10 mm ⁇ 10 mm ⁇ 200 ⁇ m to produce a positive electrode 12, and a titanium mesh was electrically connected to the positive electrode 12 as a current collector 15. And the negative electrode 11 which consists of aluminum meshes, and the positive electrode 12 which consists of biocarbon were bonded together via the separator 13 which consists of a nonwoven fabric.
- the negative electrode / separator / positive electrode laminate thus obtained was placed in a container 16 made of a PTFE film, and an electrolyte solution 17 was injected into the container 16 and sealed.
- the electrolyte solution 17 was an aqueous solution composed of 4 mol / liter NaCl and having a pH of 7. Further, phosphoric acid was added so that the final concentration was 1.0 mol, and the pH was adjusted to 7 with potassium hydroxide.
- FIG. 7 shows the result of measuring the output characteristics of the direct aluminum fuel cell of Example 3 thus produced at a cell voltage of 0.7V. Power generation continued for 3 hours or more from the start of power generation (start of discharge). The maximum current density was about 0.020 A / cm 2 , and the output was about 10 mW / cm 2 .
- the direct aluminum fuel cell of Example 3 has the same advantages as the direct aluminum fuel cell of Example 1.
- Example 4 is a modification of Example 1 to Example 3.
- the direct aluminum fuel cell of Example 4 is different from the direct aluminum fuel cells of Examples 1 to 3 in that the negative electrode 11 as the fuel is configured to be replaceable.
- Example 4 the negative electrode 11 that is a fuel is covered with a bag-like film 31 that allows the electrolytic solution 17 to pass therethrough.
- the negative electrode 11 covered with the bag-shaped film 31 is accommodated in the fuel cartridge 32, and the fuel cartridge 32 is accommodated in the fuel cartridge accommodating portion 34.
- the fuel cartridge storage portion 34 is placed on the separator 13.
- Reference numbers 33a and 33b indicate fuel pushers.
- the fuel cartridge housing portion 34 has a cartridge insertion port 34a for inserting the fuel cartridge 32 into the inside from the outside, and a cartridge ejection port 34b for taking out the fuel cartridge 32 to the outside.
- FIG. 8B shows a schematic cross-sectional view of the fuel cartridge 32 in an unused state
- FIG. 8C shows a schematic cross-sectional view of the fuel cartridge 32 after the negative electrode 11 serving as the fuel is used up
- FIG. 8D shows a schematic cross-sectional view of a direct aluminum fuel cell in a state where the negative electrode 11 is used up.
- aluminum hydroxide 35 as a by-product is confined in the bag-like film 31.
- the reference number 33c indicates an extruding spring in which both ends are fixed to the fuel extruding tools 33a and 33b.
- the fuel pusher 33a is fixed to the fuel cartridge 32, and the fuel pusher 33b presses the negative electrode 11 against the separator 13 by a spring 33c.
- the cartridge insertion port 34a is opened, an unused fuel cartridge 32 is inserted into the fuel cartridge storage portion 34, and the used fuel cartridge 32 is removed from the cartridge ejection port 34b. Extrude outside.
- the unused fuel cartridge 32 is set at a predetermined position, and the state shown in FIG. 8A is obtained.
- the negative electrode 11 is pressed against the separator 13 by the fuel pusher 33b.
- the direct aluminum fuel cell of Example 4 is the same as the direct aluminum fuel cell of Examples 1 to 3 except for the points described above.
- this indication can also take the following structures.
- pK a of the buffer substance is 4 or more, a direct aluminum fuel cell according to 10 or less [1].
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Abstract
Description
アルミニウムを含む材料を有する負極、及び、
中性付近の条件において酸素を還元する正極、
を有し、
pHが3以上、10以下の電解液が用られ、
電解液には緩衝物質が含まれる。
アルミニウムを含む材料を有する負極、及び、
中性付近の条件において酸素を還元する正極、
を有する。
1.実施例1(直接アルミニウム燃料電池、その製造方法及びその動作)
2.実施例2(実施例1の変形)
3.実施例3(実施例1の別の変形)
4.実施例4(実施例1~実施例3の変形)、その他
アルミニウムを含む材料を有する負極11、及び、
中性付近の条件において酸素を還元する正極12、
を有し、更には、負極11と正極12との間にセパレータ13が配されている。負極11の上面には集電体14が電気的に接続されており、正極12の下面には集電体15が電気的に接続されている。典型的には、負極11、正極12、及び、少なくとも負極11と正極12との間のセパレータ13の部分は、電解液に浸漬されている。セパレータ13は電解液によって満たされており、負極11と空気極12との間のアルミニウムイオンの伝導を担う電解質層を構成する。
Al3++6H2O → [Al(H2O)6]3+ (2)
[Al(H2O)6]3+ → [Al(OH)6]3-+6H+ (3)
Al3++6H2O → [Al(OH)6]3-+6H+ (4)
[1]《直接アルミニウム燃料電池:第1の態様》
アルミニウムを含む材料を有する負極、及び、
中性付近の条件において酸素を還元する正極、
を有し、
pHが3以上、10以下の電解液が用られ、
電解液には緩衝物質が含まれる直接アルミニウム燃料電池。
[2]緩衝物質のpKaは4以上、10以下である[1]に記載の直接アルミニウム燃料電池。
[3]正極は、pHが3以上、10以下の条件において酸素を還元する[1]又は[2]に記載の直接アルミニウム燃料電池。
[4]電解液はハロゲン化物イオンを含む[1]乃至[3]のいずれか1項に記載の直接アルミニウム燃料電池。
[5]ハロゲン化物イオンは塩化物イオンである[4]に記載の直接アルミニウム燃料電池。
[6]正極に酸素還元酵素が固定化されている[1]乃至[5]のいずれか1項に記載の直接アルミニウム燃料電池。
[7]正極は、炭素若しくは金属から成り、又は、触媒を含む[1]乃至[6]のいずれか1項に記載の直接アルミニウム燃料電池。
[8]正極は、中性付近の条件において酸素を4電子還元することができる触媒を含む[1]乃至[6]のいずれか1項に記載の直接アルミニウム燃料電池。
[9]触媒が酵素である[8]に記載の直接アルミニウム燃料電池。
[10]正極と負極との間にセパレータを有する[1]乃至[9]のいずれか1項に記載の直接アルミニウム燃料電池。
[11]負極は、箔状、シート状又は板状の形状を有する[1]乃至[10]のいずれか1項に記載の直接アルミニウム燃料電池。
[12]負極の少なくとも一部が、メッシュ状に形成され、又は、多孔質材料から成る[1]乃至[11]のいずれか1項に記載の直接アルミニウム燃料電池。
[13]負極はアルミニウム箔から成る[1]乃至[12]のいずれか1項に記載の直接アルミニウム燃料電池。
[14]負極は交換可能に構成されている[1]乃至[13]のいずれか1項に記載の直接アルミニウム燃料電池。
[15]負極を交換する際に、副生成物である不溶物が同時に除去可能に構成されている[14]に記載の直接アルミニウム燃料電池。
[16]《直接アルミニウム燃料電池:第2の態様》
アルミニウムを含む材料を有する負極、及び、
中性付近の条件において酸素を還元する正極、
を有する直接アルミニウム燃料電池。
[17]正極は、pHが3以上、10以下の条件において酸素を還元する[16]に記載の直接アルミニウム燃料電池。
[18]《電子機器》
[1]乃至[17]のいずれか1項に記載の直接アルミニウム燃料電池を少なくとも1つ有する電子機器。
Claims (18)
- アルミニウムを含む材料を有する負極、及び、
中性付近の条件において酸素を還元する正極、
を有し、
pHが3以上、10以下の電解液が用られ、
電解液には緩衝物質が含まれる直接アルミニウム燃料電池。 - 緩衝物質のpKaは4以上、10以下である請求項1に記載の直接アルミニウム燃料電池。
- 正極は、pHが3以上、10以下の条件において酸素を還元する請求項1に記載の直接アルミニウム燃料電池。
- 電解液はハロゲン化物イオンを含む請求項1に記載の直接アルミニウム燃料電池。
- ハロゲン化物イオンは塩化物イオンである請求項4に記載の直接アルミニウム燃料電池。
- 正極に酸素還元酵素が固定化されている請求項1に記載の直接アルミニウム燃料電池。
- 正極は、炭素若しくは金属から成り、又は、触媒を含む請求項1に記載の直接アルミニウム燃料電池。
- 正極は、中性付近の条件において酸素を4電子還元することができる触媒を含む請求項1に記載の直接アルミニウム燃料電池。
- 触媒が酵素である請求項8に記載の直接アルミニウム燃料電池。
- 正極と負極との間にセパレータを有する請求項1に記載の直接アルミニウム燃料電池。
- 負極は、箔状、シート状又は板状の形状を有する請求項1に記載の直接アルミニウム燃料電池。
- 負極の少なくとも一部が、メッシュ状に形成され、又は、多孔質材料から成る請求項1に記載の直接アルミニウム燃料電池。
- 負極はアルミニウム箔から成る請求項1に記載の直接アルミニウム燃料電池。
- 負極は交換可能に構成されている請求項1に記載の直接アルミニウム燃料電池。
- 負極を交換する際に、副生成物である不溶物が同時に除去可能に構成されている請求項14に記載の直接アルミニウム燃料電池。
- アルミニウムを含む材料を有する負極、及び、
中性付近の条件において酸素を還元する正極、
を有する直接アルミニウム燃料電池。 - 正極は、pHが3以上、10以下の条件において酸素を還元する請求項16に記載の直接アルミニウム燃料電池。
- アルミニウムを含む材料を有する負極、及び、
中性付近の条件において酸素を還元する正極、
を有し、
pHが3以上、10以下の電解液が用られ、
電解液には緩衝物質が含まれる直接アルミニウム燃料電池を少なくとも1つ有する電子機器。
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US14/397,904 US20150093657A1 (en) | 2012-05-09 | 2013-04-19 | Direct aluminum fuel cell and electronic device |
CN201380023024.2A CN104285335A (zh) | 2012-05-09 | 2013-04-19 | 直接铝燃料电池和电子设备 |
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Cited By (4)
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---|---|---|---|---|
JP2017004934A (ja) * | 2015-04-29 | 2017-01-05 | アルブフェラ エナジー ストレージ, エス.エル.Albufera Energy Storage, S.L. | アルミニウム−マンガン電気化学セル |
JP2019067618A (ja) * | 2017-09-29 | 2019-04-25 | マクセルホールディングス株式会社 | 空気電池の封入体、デバイスの封入体 |
JP2020009647A (ja) * | 2018-07-10 | 2020-01-16 | 東洋インキScホールディングス株式会社 | 酵素発電デバイス |
JP2020098683A (ja) * | 2018-12-17 | 2020-06-25 | トヨタ自動車株式会社 | 正極集電箔 |
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CN105680059A (zh) * | 2016-01-15 | 2016-06-15 | 云南星能科技股份有限公司 | 一种新型铝基负极植物电解液电池 |
US20210036288A1 (en) * | 2017-12-01 | 2021-02-04 | The University Of Hong Kong | Paper-based aluminum-air batteries and battery packs for portable applications |
CN108588444A (zh) * | 2018-04-20 | 2018-09-28 | 东深金属燃料动力实验室有限责任公司 | 将废弃铝材转变为铝燃料用于发电的方法 |
CN109980323A (zh) * | 2019-04-23 | 2019-07-05 | 陈让珠 | 石墨烯铝空气燃料电池制作方法 |
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- 2013-04-19 WO PCT/JP2013/061586 patent/WO2013168536A1/ja active Application Filing
- 2013-04-19 CN CN201380023024.2A patent/CN104285335A/zh active Pending
- 2013-04-19 JP JP2014514428A patent/JPWO2013168536A1/ja active Pending
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WO2004112174A1 (ja) * | 2003-06-11 | 2004-12-23 | Matsushita Electric Industrial Co., Ltd. | 酸素還元用電極の製造方法ならびに酸素還元用電極及びそれを用いた電気化学素子 |
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JP2017004934A (ja) * | 2015-04-29 | 2017-01-05 | アルブフェラ エナジー ストレージ, エス.エル.Albufera Energy Storage, S.L. | アルミニウム−マンガン電気化学セル |
JP2019067618A (ja) * | 2017-09-29 | 2019-04-25 | マクセルホールディングス株式会社 | 空気電池の封入体、デバイスの封入体 |
JP2020009647A (ja) * | 2018-07-10 | 2020-01-16 | 東洋インキScホールディングス株式会社 | 酵素発電デバイス |
JP7135516B2 (ja) | 2018-07-10 | 2022-09-13 | 東洋インキScホールディングス株式会社 | 酵素発電デバイス |
JP2020098683A (ja) * | 2018-12-17 | 2020-06-25 | トヨタ自動車株式会社 | 正極集電箔 |
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US20150093657A1 (en) | 2015-04-02 |
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